Novel stereoretentive ruthenium complexes, methods for their preparation, intermediates used in the methods and use of the novel stereoretentive ruthenium complexes in olefin metathesis reactions - Patents.com

Abstract

The subject of the present invention are stereoretaining ruthenium complexes of the general formula 1a-Ru and / or 1b-Ru, in which all variables have the meanings defined in the specification. The subject of the present invention is also a process for the preparation of ruthenium complexes, intermediates used in the process for the preparation of ruthenium complexes, and the use of said ruthenium complexes as (pre)catalysts in olefin metathesis, in ring-closing metathesis (RCM), homometathesis (self-CM) and stereoretaining processes. JPEG2025504619000115.jpg32100

Description

[Technical field]

[0001] The subject of the present invention relates to novel stereoretentive ruthenium complexes useful as catalysts and / or (pre)catalysts for olefin metathesis reactions, and their use in olefin metathesis reactions. The subject of the present invention is also intermediates used to generate the novel stereoretentive ruthenium complexes, as well as methods for generating the novel stereoretentive ruthenium complexes. The present invention has been found as a desirable universal tool in organic synthesis, whose application depends on the C=C bond configuration in the substrate in the selective synthesis of olefins of Z- or E-configuration.

[0002] In recent years, great progress has been made in the application of olefin metathesis in organic synthesis [Non-Patent Document 1]. Many homogeneous ruthenium-based olefin metathesis catalysts are known in the art, which combine high activity in various types of metathesis reactions with high tolerance to functional groups found in the substrates / products. This combination of features makes metathesis catalysts an important player in modern organic synthesis and industry. The (pre)catalysts most frequently described in the literature are Grubbs-type, Hoveyda-type and indenylidene complexes with carbene N-heterocyclic carbene ligands (NHC) in their structure, and more recently Bertrand-type catalysts with cyclic alkylaminocarbene ligands (CAAC) [Non-Patent Document 2; Patent Document 1]. The majority of the structures of other olefin metathesis catalysts are derived from these above-mentioned ruthenium complexes.

[0003] [ka]

[0004] In the application of olefin metathesis in modern organic synthesis, the control of C=C double bond configuration is of great importance. The first literature report of a Z-selective ruthenium catalyst for olefin metathesis was in 2011 [Non-Patent Document 3]. In this scientific paper, Grubbs et al. reported the synthesis of symmetric (Gru-Mes) and asymmetric (Gru-Ada-1) NHC ligands with mesyl and adamantyl substituents at the nitrogen atom, as well as anionic ligands of pivalic acid ( t BuCOO - ) was described. Later, Professor Grubbs' team obtained similar structures (Gru-Ada-2, Gru-Ada-3) in which the anionic ligand was a nitro acid residue [Non-Patent Document 4]. These catalysts showed high chemoselectivity towards terminal C=C double bonds and selectively formed products with Z configuration in olefin metathesis reactions. In the presence of an internal (non-terminal) C=C bond in the E configuration in the substrate structure, the olefin metathesis reaction did not proceed, despite high loading of the ruthenium catalyst and long reaction times (1 mol%, 5 h, RT, THF).

[0005] [ka]

[0006] Subsequent improvements in ruthenium catalysts involve Hoveyda-Grubbs type complexes, in which the two anionic ligands are replaced by dithiocatechol bidentate ligands [Patent Document 2 and Non-Patent Document 5].

[0007] [ka]

[0008] The principle of action of the above complexes is based on the retention (preservation) of the double bond configuration in the reaction products. Grubbs et al. [Non-Patent Document 6] showed that the use of Hov-SS-Cl2 complexes in the metathesis reaction of Z-5-tetradecene gives two products with only Z-configured double bonds, whereas the use of E-5-tetradecene as substrate in the same reaction results in exclusively E-configured olefins. In other words, catalysts containing various modifications of the dithiocatechol ligand (Hov-SS, Hov-SS-Cl2, Hov-SS-F4) are characterized by high stereoretention, i.e. the ability to transmit the original configuration of the C=C double bond from the substrate to the product of the olefin metathesis reaction.

[0009] The chelate catalysts with various modifications of the dithiocatechol ligand show high chemoselectivity and high yields of the desired products compared to the previous complexes reported by Grubbs. Notably, the reactions were carried out at room temperature with high catalyst loadings and long catalyst contact times with the substrate / product (up to 12 h in THF at room temperature, 1 mol%). The activity of the ruthenium dithiocatechol catalysts in ROMP and rare ROM / CM reactions is the first reported in the literature, so it was difficult to compare the activity of the new catalysts with those previously reported.

[0010] In a 2017 patent document [Patent Document 3], California researchers claim a list of 53 ruthenium complexes containing dianionic dithiocatechol ligands or their derivatives. All of the ruthenium compounds in this document contain chelating benzylidene and NHC ligands and are symmetrically or asymmetrically substituted at the nitrogen atom of the NHC ligand. However, not all of the claimed ruthenium compounds have been obtained or well characterized by comparative olefin metathesis reactions.

[0011] [ka]

[0012] In another patent from 2018 [Patent Document 4], the authors obtained and characterized ruthenium complexes containing chelating benzylidene ligands activated by electron-withdrawing groups. The ruthenium catalysts contained bidentate dithiocatechol derivatives and NHC or CAAC ligands. The new E5 and E8 complexes in model reactions proved to be slightly more active, with the same Z-selectivity, compared to previously known stereoretentive ruthenium complexes.

[0013] [ka]

[0014] In another patent [Patent Document 5], authors from the California company Materia Inc. describe an alkylidene ruthenium complex (C785) containing a dithiocatechol ligand and dimethylsulfoxide. SS , C885 SS ) was obtained. One of these complexes, C785 SS was investigated in a model olefin metathesis reaction (cis-5-tetradecene homometathesis) without comparison with other known stereoretentive ruthenium complexes.

[0015] [ka]

[0016] The authors of the present invention have developed a ruthenium complex (C885) that is a non-benzylidene derivative of the ruthenium catalyst (i.e., not a Hoveyda-Grubbs type complex). SS It is noteworthy that these complexes predict the stereoretention of 1,2-diphenylphosphine (Phosphosphine) in the presence ...

[0017] The high price of dithiocatechol derivatives, especially those substituted with halogen, and the long synthetic routes of other derivatives, which give the expected products in low yields, are important problems in the art. These characteristics are obstacles to the further development of stereoselective and / or stereoretentive catalysts. It is difficult to obtain new ruthenium catalysts for olefin metathesis with dithiocatechol-based ligands of planned properties by chemical synthesis and is becoming economically unreasonable for industrial scale-up.

[0018] In the search for new ruthenium complexes with high catalytic activity and improved selectivity to obtain the desired Z- or E-isomers, it is important to have convenient synthetic routes to these compounds based on readily available and inexpensive substrates, as well as a growing library of ligands that provide an alternative and / or improved source of structures for ruthenium complexes to be used as catalysts in stereoretentive olefin metathesis.

[0019] Another problem is the low thermal stability of E-selective metathesis catalysts known in the art, especially Z-selective metathesis catalysts. As a result, currently used ruthenium E- / Z-selective complexes require the use of very high catalyst loadings to obtain the desired products in high yields. An example is a paper by Grubbs et al. in 2013, which describes the possibility of synthesizing macrocycles with double bonds in the Z configuration by ring-closing metathesis with Z-selective complexes [Non-Patent Document 7]. In this work, the authors use 7.5 mol % of the catalyst dissolved in 1,2-dichloroethane at 60 °C to obtain macrocycles in 30-75% yield, with the Z isomer content in the product varying between 64 and 94%. In a study by Meyer and co-authors on macrocyclization and entropy-driven polymerization by ring-opening metathesis, as much as 10 mol % of the catalyst is needed to obtain highly functionalized macrocycles in 88% yield and with 88% Z isomer content [Non-Patent Document 8]. Z-selective complexes of other transition metals, such as molybdenum, are already characterized by a low stability at room temperature, but this problem is also solved by using high loadings (up to 10 mol%) of these complexes [9;10]. Obviously, this increases the cost of the synthesis process and contaminates the final product with harmful transition metals.

[0020] Unexpectedly, it has been found that 1,2-dithio derivatives of pyrazine, quinoxaline, their derivatives, and other similar organic compounds function as ligands for new stereoretentive ruthenium catalysts and / or (pre)catalysts for olefin metathesis.

[0021] Furthermore, it was unexpectedly found that the new olefin metathesis (pre)catalyst in the model reaction exhibited stereoretention even under conditions of rather high temperature. The stereoselective and stereoretentive ruthenium and molybdenum olefin metathesis catalysts known in the art only retain their properties under low temperature conditions (usually room temperature), which is a great difficulty and inconvenience for large organic compounds with many functional groups in the structure.

[0022] Furthermore, it was unexpectedly discovered that the addition of a zinc complex has a positive effect on the activity and selectivity of the novel stereoretentive ruthenium complex in metathesis reactions, allowing higher yields and / or selectivities to be obtained compared to reactions carried out without the addition of a zinc complex. [Prior art documents] [Patent documents]

[0023] [Patent Document 1] International Publication No. 2017 / 055945 [Patent Document 2] International Publication No. 2014 / 201300 [Patent Document 3] International Publication No. 2017 / 100585 [Patent Document 4] International Publication No. 2018 / 087230 [Patent Document 5] International Publication No. 2018 / 038928 [Non-patent literature]

[0024] [Non-Patent Document 1] RH Grubbs (Ed.), AG Wenzel (Ed.), DJ O'Leary (Ed.), E. Khosravi (Ed.), Handbook of Olefin Metathesis, 2nd. edition, 3 volumes 2015, Wiley-VCH Verlag GmbH & Co. KGaA, 1608 pages [Non-Patent Document 2] Grubbs et al. Chem. Rev., 2010, 110, 1746-1787 [Non-Patent Document 3] Grubbs et al. J. Am. Chem. Soc., 2011, 133, 8525-8527 [Non-Patent Document 4] Grubbs et al. Angew. Chem. Int. Ed., 2013, 52, 9001-9004 [Non-Patent Document 5] A. Hoveyda et al., J. Am. Chem. Soc., 2013, 135, 10258-10261 [Non-Patent Document 6] Org. Lett. 2016, 18, 772-775, DOI: 10.1021 / acs.orglett.6b00031 [Non-Patent Document 7] V. M. Marx, M. B. Herbert, B. K. Keitz, R. H. Grubbs, J. Am. Chem. Soc. 2013, 135, 94-97, DOI: 10.1021 / ja311241q [Non-Patent Document 8] A. L. Short, C. Fang, J. A. Nowalk, R. M. Weiss, P. Liu, T. Y. Meyer, ACS Macro Lett. 2018, 7, 858-862, DOI: 10.1021 / acsmacrolett.8b00460 [Non-Patent Document 9] M. Yu, C. Wang, A. F. Kyle, P. Jakubec, D. J. Dixon, R. R. Schrock, A. H. Hoveyda, Nature 2011, 479, 88-93, DOI: 10.1038 / nature10563 [Non-Patent Document 10] H. Zhang, E. C. Yu, S. Torker, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2014, 136, 16493-16496 DOI: 10.1021 / ja510768c [Summary of the Invention]

[0025] The present invention relates to a ruthenium complex of Formula 1-Ru. [ka] (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC), or a phosphine; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl, C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form quaternary ammonium, tertiary sulfonium, or quaternary phosphonium groups; or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N +R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which ring may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus; R 13 and R 14 are independently hydrogen, halogen, or optionally substituted C-C 25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C3-C 25 Cycloalkynyl, optionally substituted C-C 25 Alkoxy, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxy, optionally substituted C6-C 25Aralkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxy, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus-containing 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents, taken together, are C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycles, which may be selected from the group consisting of hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C 25 Aryl, C5-C 25 Aryloxy, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxy, C5-C 25 optionally substituted with one and / or more substituents independently selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents are independently preferably hydrogen, and / or independently hydrogen, halogen, C-C 25 Alkyl groups, C2-C 25Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R”3), carboxyl group (-COOH), ester group (-COOR”), amide group (-CONR”2), amide group (-NR”C(O)R”), formyl group (-CHO), ketone group (-COR”), thioamide group (-CSNR”2), thioketone group (-CSR”), thioester group (-CSOR”), thioester group (-COSR”), dithioester group (-CS2R”). 25 aryl, where the R groups are independently hydrogen, C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl, and the two R groups together form a C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 A heterocycloalkyl ring may be formed, optionally further comprising C1-C 12 R" is substituted with an alkyl group, or R" is a ketone group (-COR c )(R c is C1-C 12 perfluoroalkyl) or alkoxy groups (-OR d )(R d is C1-C 12 Alkyl or C3-C containing nitrogen, oxygen or sulfur 12 Heterocycloalkyl, optionally C1-C 12 substituted with an alkyl group; G is -L2 Ligand [ka] In the formula, R 20 and R 21 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen, halogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl, C5-C 20 Heteroaryl, C1-C 12 Alkoxy, C5-C 24 Aryloxy groups, C5-C 20 and / or more substituents selected from the group including heteroaryloxy, alkoxy groups (-OR"), sulfide groups (-SR"), and amine groups (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C 24 Aryl, C7-C 24 aralkyl or R 20 and R 21 Together, we will create C5-C 25 Forming a ring; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C 12alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25 heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNR c 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally further comprising C-C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C 20Aryl group or C5-C 20 Perfluoroaryl or amine groups (-NR e 2) where each R d are independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are optionally linked together to form a C4-C 10 Cyclic or C4-C 12 may form polycyclic ring systems; Each R 28 , R 29 , and R 30 The substituents are independently C-C 25 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30together, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or -1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C24 heteroaryloxy, 3- to 12-membered heterocycle, and optionally substituted with acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), or dithioester (-CS2R') groups, where the R' groups are independently selected from C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14 Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a -CH2-, -CHR'-, or -CR'2- methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -2 heteroatoms R' is a methylidene optionally substituted with a substituent R'; 25 Alkyl, C1-C 25 Perfluoroaryl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 It is optionally substituted with a group selected from heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR'2), sulfonic acid group (-SO2R'), formyl group (-COH), etc., where R' is acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-CO C1-C OR'), ester (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS2R') groups. 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, where R' is a C-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14 Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a (CH2)-, -(CHR')-, or (CR'2)-methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -3 heteroatoms halogen, and the dashed line represents the heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N +R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 Perfluoroaryl etc.)

[0026] Preferably, neutral L 1 The ligand has a structure represented by a general formula selected from any of 2a, 2b, 2c, or 2d. [ka] (In the formula: R 20 and R 21 Each substituent is independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen, halogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20Heteroaryl groups, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 and / or a group including heteroaryloxy, halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, and amino group (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C7 alkyl, C8-C9 alkyl, C10-C11 alkyl, C12-C13 alkyl, C14-C15 alkyl, C16-C17 alkyl, C18-C19 alkyl, C19-C21 alkyl, C19-C22 alkyl, C19-C23 alkyl, C19-C24 alkyl, C19-C25 alkyl, C20-C26 alkyl, C21-C27 alkyl, C22-C31 alkyl, C23-C32 alkyl, C24-C33 alkyl, C25-C41 alkyl, C25-C41 alkyl, C26-C41 alkyl, C27-C42 alkyl, C28-C43 alkyl, C29-C54 alkyl, C31-C55 alkyl, C32-C65 alkyl, C31-C75 alkyl, C31-C41 alkyl, C31-C42 alkyl, C31-C43 alkyl, C31-C44 alkyl, C31-C45 ... 24 Aryl, C7-C 24 aralkyl or R 20 and R 21 Together they form the ring C5-C 25 Forming a base; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C 12 alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25 heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNRc 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally further comprising C-C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C 20 Aryl group or C5-C 20 Perfluoroaryl or amine groups (-NR e 2) where each R d are independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked together to form a cyclic C-C 10 C4-C or polycyclic 12 A system may be formed; R 28 , R 29 , and R 30 The substituents are independently C-C 25 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 together, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Form a system.)

[0027] Preferably, the subject of the invention is a ruthenium complex of formula 1a-Ru. [ka] (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a phosphine; n' is 1 or 0. Z is selected from the group including halogen, O, S, Se, or NR′″ groups, where R′″ is methylidene, C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR'2), sulfonic acid group (-SO2R'), formyl group (-COH), where R' is a C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, or halogen, and when Z is halogen, R 15 does not exist; R 1 and R2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 Heteroaryloxy, C1-C 25 Alkyl groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; R 15 are independently hydrogen, C1-C 25 Alkyl, C1-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 24 aryloxy, -COOR", CHCOOR", -CONR", -CHCONR", -COR", -CHCOR", -CHCON(OR"")(R"), -CHCON(OR"")(R"), or halogen, where R"' is a C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl, C6-C 20 aryl, which are at least one C-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C6-C 24 optionally substituted by aryloxy, or halogen; R 16 , R 17 , R 18 , and R 19 are independently hydrogen, halogen, C1-C 25 Alkyl groups, C2-C 25 Alkenyl groups, C5-C 25Aryl groups, alkoxy groups (-OR"), sulfide groups (-SR"), sulfoxide groups (-S(O)R"), sulfonium groups (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSRR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl, where R 16 , R 17 , R 18 , and R 19 The substituents, taken together, form a substituted or unsubstituted cyclic C4-C 10 or polycyclic C4-C 12 A system may be formed.)

[0028] Preferably, the subject of the invention is a ruthenium complex of formula 1b-Ru. [ka] (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a PR3 phosphine; L 2is a neutral ligand selected from N-heterocyclic carbene (NHC), cyclic alkylaminocarbene (CAAC), PR3 phosphine derivatives or pyridine derivatives; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P+ R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 R forms a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; 13 and R 14 are independently hydrogen, halogen, or optionally substituted C-C 25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C3-C 25 Cycloalkynyl, optionally substituted C-C 25 Alkoxy, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxy, optionally substituted C6-C 25 Arylalkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxy, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus-containing 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents, taken together, are C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus-containing 3- to 12-membered heterocycles, which may be selected from the group consisting of hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C 25 Aryl, C5-C 25 Aryloxy, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxy, C5-C 25 may be independently substituted with one or more substituents selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycle.

[0029] Preferably, the subject of the invention is a ruthenium complex of formula 1b-Ru. [ka] (In the formula, L 1 The ligand is [ka] (In the formula: R 20 and R 21Each substituent is independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen, halogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 and / or a group including heteroaryloxy, halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, and amino group (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C7 alkyl, C8-C9 alkyl, C10-C11 alkyl, C12-C13 alkyl, C14-C15 alkyl, C16-C17 alkyl, C18-C19 alkyl, C19-C21 alkyl, C19-C22 alkyl, C19-C23 alkyl, C19-C24 alkyl, C19-C25 alkyl, C20-C26 alkyl, C21-C27 alkyl, C22-C31 alkyl, C23-C32 alkyl, C24-C33 alkyl, C25-C41 alkyl, C25-C41 alkyl, C26-C41 alkyl, C27-C42 alkyl, C28-C43 alkyl, C29 24 Aryl, C7-C 24 aralkyl or R 20 and R 21 Together they form the ring C5-C 25 Forming a base; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C 12 alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 Perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNR c 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may optionally further comprise any of C1-C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C 20 Aryl group or C5-C 20 Perfluoroaryl or amine groups (-NR e 2) where each R dare independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked together to form a cyclic C-C 10 C4-C or polycyclic 12 A system may be formed; R 28 , R 29 , and R 30 The substituents are independently C-C 25 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , and R 30 together, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 (form a system) and In the formula, L 2 The ligand is [ka] (In the formula, each R 20 and R 21 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 and / or a group including heteroaryloxy, halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, and amino group (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C7 alkyl, C8-C9 alkyl, C10-C11 alkyl, C12-C13 alkyl, C14-C15 alkyl, C16-C17 alkyl, C18-C19 alkyl, C19-C21 alkyl, C19-C22 alkyl, C19-C23 alkyl, C19-C24 alkyl, C19-C25 alkyl, C20-C26 alkyl, C21-C27 alkyl, C22-C31 alkyl, C23-C32 alkyl, C24-C33 alkyl, C25-C41 alkyl, C25-C41 alkyl, C26-C41 alkyl, C27-C42 alkyl, C28-C43 alkyl, C29 24 Aryl, C7-C 24 aralkyl or R 20 and R 21 Together they form the ring C5-C 25 Forming a base; Each R 20 , R 21 , R 22 , R 23 , R24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C 12 alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25 heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-COR d ) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNR c 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally further comprising C-C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C 20 Aryl group or C5-C 20 Perfluoroaryl or amine groups (-NR e 2) where each R d are independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked together to form a cyclic C-C 10 C4-C or polycyclic 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently hydrogen, halogen, C1-C 25 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 together, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently hydrogen, halogen, C1-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; R 13 and R 14are independently hydrogen, halogen, or optionally substituted C-C 25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C3-C 25 Cycloalkynyl, optionally substituted C-C 25 Alkoxy, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxy, optionally substituted C6-C 25 Arylalkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxy, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents, taken together, are C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus-containing 3- to 12-membered heterocycles, which may be selected from the group consisting of hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C 25 Aryl, C5-C 25 Aryloxy, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxy, C5-C 25 perfluoroaryl, 3- to 12-membered heterocycle, It is.)

[0030] Preferably, the subject of the invention is a ruthenium complex represented by a formula chosen from the following: [ka] JPEG2025504619000017.jpg190152 JPEG2025504619000018.jpg236152

[0031] A subject of the invention is also compounds of structure defined in formula 3a or 3b. [ka] (In the formula, M is a monovalent or divalent metal cation; n is 0, 1, 2 or 3; E is a group, or multiple groups if the heteroatom is nitrogen or phosphorus: C1-C 25 Alkyl groups, C1-C 25 Cycloalkyl groups, C5-C 20 Alkoxy groups, C5-C 20 Aryl groups C7-C 20 Aralkyl groups, C5-C 24 Aryloxy groups, C2-C 12 Alkenyl groups, C6-C 20 Heteroaryl groups, C5-C 24At least one heteroatom selected from the group including oxygen, sulfur, selenium, nitrogen, phosphorus, substituted with a heteroaryloxy group or hydrogen, and these groups are at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or, when two identical or different heteroatoms form a chelating system, together they form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Forming the system, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N +R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; or R 1 and R 2 Together, they form substituted or unsubstituted C4-C 10 cyclic, C4-C 12 Polycyclic, C4-C 10 Aromatic, C4-C 10 Heteroaromatic, C4-C 10 Polycyclic aromatics, and C4-C 10 They form polycyclic heteroaromatic systems, which contain hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 Forming a ring, the ring may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus.

[0032] Preferably, a subject of the invention is a compound of formula 3c or 3d or 3e. [ka] (In the formula, M 2+ are Zn, Cu, Mg, and Ca cations, M + is Li, Na, K, Cs, Cu or Cu×(E)n is a cation, n is 1 or 2; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 , polycyclic aromatic C4-C 10 , and polycyclic heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, C1-C 25 Alkyl, C1-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 or two selected R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10, R 11 and R 12 The substituents, taken together, form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , heterocyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These are hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 and optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen.

[0033] Preferably, the subject of the present invention is compound 3f. [ka] (In the formula, M 2+ is a Zn cation, R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S +R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24Aryloxy groups, C5-C 20 Heteroaryloxy groups, C1-C 25 Alkyl groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 Forming a ring, the ring may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus.

[0034] Preferably, the subject of the present invention is a compound whose structure is represented by a formula selected from 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13 and 3-K1, etc.: [ka]

[0035] The subject of the present invention is also compounds of formula 1-Ru as defined above: [ka] (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC), or a phosphine; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; or R 1 and R 2 together form a substituted or unsubstituted cyclic C4-C 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 These form the system: hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N +R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; R 13 and R 14 are independently hydrogen, halogen, or optionally substituted C-C 25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C3-C 25 Cycloalkynyl, optionally substituted C-C 25 Alkoxy, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxy, optionally substituted C6-C 25Arylalkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxy, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents, taken together, are C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycles, which may be selected from the group consisting of hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C 25 Aryl, C5-C 25 Aryloxy, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxy, C5-C 25 optionally substituted with one and / or more substituents independently selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents are independently preferably hydrogen, and / or independently hydrogen, halogen, C-C 25 Alkyl groups, C2-C 25Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R”3), carboxyl group (-COOH), ester group (-COOR”), amide group (-CONR”2), amide group (-NR”C(O)R”), formyl group (-CHO), ketone group (-COR”), thioamide group (-CSNR”2), thioketone group (-CSR”), thioester group (-CSOR”), thioester group (-COSR”), dithioester group (-CS2R”). 25 aryl, where the R groups are independently hydrogen, C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl, and the two R groups together form a C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 A heterocycloalkyl ring may be formed, optionally further comprising C1-C 12 R" is substituted with an alkyl group, or R" is a ketone group (-COR c )(R c is C1-C 12 perfluoroalkyl) or alkoxy groups (-OR d )(R d is C1-C 12 Alkyl or C3-C containing nitrogen, oxygen or sulfur 12 Heterocycloalkyl, optionally C1-C 12 substituted with an alkyl group; G is -L2 Ligand [ka] In the formula, R 20 and R 21 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 and / or a heteroaryloxy group, each of which may be independently substituted with one or more substituents selected from the group including halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, and amine group (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C 24 Aryl, C7-C 24 aralkyl or R 20 and R 21 Together, we will create C5-C 25 Forming a ring; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C12 alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25 heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNR c 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally further comprising C-C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C20 Aryl group or C5-C 20 Perfluoroaryl or amine groups (-NR e 2) where each R d are independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12 may be substituted with an alkyl group, R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are optionally linked together to form a C4-C 10 Cyclic or C4-C 12 may form polycyclic ring systems; Each R 28 , R 29 , and R 30 The substituents are independently C-C 25 Alkyl, C1-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 together, hydrogen, C1-C12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or -1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24and optionally substituted with an acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS2R') group, wherein R' group is C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14 Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a (CH2)-, -(CHR')-, or (CR'2)-methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -2 heteroatoms methylidene optionally substituted with hydrogen, R' substituents, C1-C 25 Alkyl, C1-C 25 Perfluoroaryl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 It is optionally substituted with a group selected from heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR'2), sulfonic acid group (-SO2R'), formyl group (-COH), etc., where R' is acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester, etc. C1-C optionally substituted with ter (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS2R') groups; 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, where R' is a C-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20Heteroaryl or C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14 Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a (CH2)-, -(CHR')-, or (CR'2)-methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -3 heteroatoms halogen, and the dashed line represents the heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N +R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 Perfluoroaryl etc.) A method for producing a ruthenium complex of the formula: Formula 4-Ru: [ka] (In the formula: X 1 and X 2 are independently halogen anions, -CN, -SCN, -OR a , -SR a , -O(C=O)R a , -O(SO2)R a , and -OSi(R a )3, where R a is C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl or C5-C 20 Aryl, having at least one C-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 optionally substituted with heteroaryloxy or halogen; L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a phosphine; R 13 and R 14 are independently hydrogen, halogen, or optionally substituted C-C 25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C3-C 25 Optionally substituted C-C cycloalkynyl 25 Alkoxy, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxy, optionally substituted C6-C 25 Arylalkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxy, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus-containing 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents, taken together, are C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium or phosphorus-containing 3- to 12-membered heterocycles; hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C 25 Aryl, C5-C 25 Aryloxy, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxy, C5-C 25 may be independently substituted with one and / or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents are independently preferably hydrogen and / or hydrogen, C-C 25 Alkyl groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R”3), carboxyl group (-COOH), ester group (-COOR”), amide group (-CONR”2), amide group (-NR”C(O)R”), formyl group (-CHO), ketone group (-COR”), thioamide group (-CSNR”2), thioketone group (-CSR”), thionoester group (-CSOR”), thioester group (-COSR”), dithioester group (-CS2R”). 25 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; G is -L 2 Ligand [ka] In the formula, R 20 and R 21 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl groups, or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 and / or a heteroaryloxy group, each of which may be independently substituted with one or more substituents selected from the group including halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, and amine group (-NR"2), where the R" groups are independently selected from hydrogen, C1-C5 alkyl, C6-C 24 Aryl, C7-C 24 aralkyl or R20 and R 21 Together, we will create C5-C 25 Forming a ring; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl, C1-C 12 Alkoxy groups, hydroxymethyl groups (-CHOH), amine groups (-NR a 2) C1-C optionally substituted with 12 An alkyl group (wherein each R a are independently hydrogen or C1-C 12 alkyl or two R a The groups, together, are C3-C 12 Cycloalkyl ring or C3-C 25 heterocycloalkyl), C3-C 12 Cycloalkyl group; C5-C 20 Aryl groups, C5-C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH2OCOR b ), where R b is C5-C 20 Aryl group or C5-C 20 perfluoroaryl groups; amine groups (-NR c 2) Methylamine group (-CHNR c 2) where each R c are independently hydrogen or C1-C 12 alkyl or two R c The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally further comprising C-C 12and wherein the heteroatoms present in the heterocycle are substituted with one or two C-C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, halogen, C1-C 12 C3-C optionally substituted with alkyl groups 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) groups, where R d is C5-C 20 Aryl group or C5-C 20 Perfluoroaryl groups, or amino groups (-NR e 2) where each R d are independently hydrogen or C1-C 12 alkyl, and two R e The groups, together, are C3-C 12 Cycloalkyl ring or C3-C containing nitrogen, oxygen or sulfur 25 Heterocycloalkyl may be formed, optionally C-C 12 further substituted with an alkyl group, where the heteroatoms present in the heterocycle are one or two C-C heteroatoms forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group; 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked together to form a cyclic C-C 10 C4-C or polycyclic 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently C-C 25 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl, or C5-C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 together, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 A substituted or unsubstituted cyclic C4-C alkyl group, optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen. 10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently C-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, which are hydrogen, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24Aryloxy groups, C5-C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or -1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 and optionally substituted with an acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS2R') group, wherein R' group is C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20Heteroaryl, or C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14 Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a -CH2)-, -CHR'-, or -CR'2-methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -2 heteroatoms methylidene optionally substituted with hydrogen, R' substituents, C1-C 25 Alkyl, C1-C 25 Perfluoroaryl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24Heteroaryloxy, 3-12 membered heterocycle, acyl group (-COR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate (-CONR'2), sulfonic acid (-SO2R'), formyl (-COH), etc., optionally substituted with a group selected from the group R', acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester C1-C optionally substituted with (-CH2COOR'), ester (-CHR'COOR'), ester (-C(R')2COOR'), amide (-CONR'2), sulfonic acid (-SO2R'), formyl (-COH), sulfonamide (-SO2NR'2), ketone (-COR'), thioamide (-CSNR'2), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS2R') groups. 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, where R' is a C-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and the R 14Represents a direct bond to a substituent or R 14 represents a connection between a substituent and a heteroatom via a (CH2)-, -(CHR')-, or (CR'2)-methylene bridge, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + C5-C alkyl groups each substituted with 1 to 4 substituents independently selected from the group consisting of R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), and dithioester group (-CS2R″). 15aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 is a perfluoroaryl; or -3 heteroatoms halogen, and the dashed line represents a heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxy, 3-12 membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), a carboxyl group (-COOH), an ester group (-COOR″), an amide group (-CONR″2), an amide group (-NR″C(O)R″), a formyl group (-CHO), a ketone group (-COR″), a thioamide group (-CSNR″2), a thioketone group (-CSR″), a thionoester group (-CSOR″), a thioester group (-COSR″), and a dithioester group (-CS2R″). 15 aryl, where R groups are C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 Perfluoroaryl etc.) with an alkylidene ruthenium complex of formula 3a or 3b: [ka] (In the formula, M is a monovalent or divalent metal cation; n is 0, 1 or 2; E is a group, or multiple groups if the heteroatom is nitrogen or phosphorus: C1-C 25 Alkyl groups, C1-C 25 Cycloalkyl groups, C5-C 20 Alkoxy groups, C5-C 20 Aryl groups C7-C 20 Aralkyl groups, C5-C 24 Aryloxy groups, C2-C 12 Alkenyl groups, C6-C 20 Heteroaryl groups, C5-C 24 At least one heteroatom selected from the group including oxygen, sulfur, selenium, nitrogen, phosphorus, substituted with a heteroaryloxy group or hydrogen, and these groups are at least one C-C 12 Alkyl or C1-C 12 Optionally substituted by perfluoroalkyl or, when two identical or different heteroatoms form a chelating system, together they form a substituted or unsubstituted cyclic C4-C10 , polycyclic C4-C 12 , aromatic C4-C 10 , Heteroaromatic C4-C 10 Forming the system, hydrogen, C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxy, C5-C 24 Aryloxy, C5-C 20 optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen; R 1 and R 2 are independently hydrogen, halogen, C1-C 25 Alkyl, C5-C 20 Alkoxy, C5-C 20 Aryl, C7-C 20 Aralkyl, C5-C 24 Aryloxy, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 heteroaryloxy, which have at least one C1-C 12 Alkyl or C1-C 12 or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P +R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thionoester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), where R″ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 ... 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C1-C 12 and optionally substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C-C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; or R 1 and R 2 Together, they form substituted or unsubstituted C4-C 10 cyclic, C4-C 12 Polycyclic, C4-C 10 Aromatic, C4-C 10 Heteroaromatic, C4-C 10 Polycyclic aromatics, and C4-C 10 They form polycyclic heteroaromatic systems, which contain hydrogen, halogens, C1-C 25 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy groups, C5-C 20 Heteroaryloxy groups, C2-C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S +R″2), sulfonyl group (-SO2R″), sulfonamide group (-SO2NR″2), amine group (-NR″2), ammonium group (-N + R”3), nitro group (-NO2), cyano group (-CN), phosphonate group (-P(O)(OR”)2), phosphinate group (-P(O)R”(OR”)), phosphonite group (-P(OR”)2), phosphine group (-PR”2), phosphine oxide group (-P(O)R”2), phosphonium group (-P + R″3), carboxyl group (-COOH), ester group (-COOR″), amide group (-CONR″2), amide group (-NR″C(O)R″), formyl group (-CHO), ketone group (-COR″), thioamide group (-CSNR″2), thioketone group (-CSR″), thioester group (-CSOR″), thioester group (-COSR″), dithioester group (-CS2R″), wherein the R″ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C7 alkyl, C8-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl, C1-C14 alkyl, C1-C16 alkyl, C1-C18 alkyl, C1-C19 alkyl, C2-C22 alkyl, C2-C24 alkyl, C2-C25 alkyl, C2-C26 alkyl, C2-C28 alkyl, C2-C29 alkyl, C2-C30 alkyl, C2-C31 alkyl, C2-C32 alkyl, C2-C33 alkyl, C2-C34 alkyl, C2-C35 alkyl, C2-C36 alkyl, C2-C37 alkyl, C2-C38 alkyl, C2-C39 alkyl, C2-C40 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C55 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl, C2-C41 alkyl, C2-C42 alkyl, C2-C43 alkyl, C2-C44 alkyl, C2-C45 alkyl, C2-C45 alkyl, C2-C46 alkyl, C2-C47 alkyl, C2-C48 alkyl, C2-C49 alkyl, C2-C49 alkyl 24 Aryl, C7-C 24 Aralkyl, C5-C 24 perfluoroaryl or the two R groups together form a C5-C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; with a compound of the structure defined as

[0036] The present invention also relates to the use of compounds of formula 1-Ru as precatalysts and / or catalysts in olefin metathesis reactions, in particular ring-closing metathesis (RCM), cross metathesis (CM), homometathesis (cross metathesis between two molecules of the same olefin), ethenolysis, isomerization, diastereoselective ring rearrangement metathesis (DRRM) reactions, alkene-alkyne (ene-yne) metathesis or ROMP and ADMET type polymerization reactions.

[0037] Preferably, the olefin metathesis reaction is carried out using a 1-Ru catalyst and / or pre-catalyst in the presence of a compound having a structure represented by a formula selected from 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13, 3-K1, etc. in an amount ranging from 0.0001 mol % to 200 mol %.

[0038] Preferably, the reaction is carried out in an organic solvent such as toluene, benzene, mesitylene, hexane, dichloromethane, dichloroethane, chlorobenzene, perfluorobenzene, perfluorotoluene, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, methyl tert-butyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2-Me-THF, 4-Me-THP, dioxane, DME, PAO, PEG, paraffin, esters of saturated fatty acids, and the like.

[0039] Preferably, the reaction is carried out in a solvent-free system.

[0040] Preferably, the reaction is carried out at a temperature of from 20 to 200°C.

[0041] Preferably, the reaction is carried out for a period of from 5 minutes to 48 hours.

[0042] Preferably, the 1-Ru compound is used in an amount of 10 mol % or less.

[0043] Preferably, the 1-Ru compound is used in an amount of 0.1 mol % or less.

[0044] Preferably, the 1-Ru compound is added to the reaction mixture in portions in solid form and / or continuously by means of a pump as a solution in an organic solvent.

[0045] Preferably, the gaseous by-products of the reaction selected from ethylene, propylene, butylene are actively removed from the reaction mixture using inert gas barbotage or vacuum.

[0046] The subject matter of the present invention is illustrated in the embodiments shown in the drawings. [Brief description of the drawings]

[0047] [Figure 1] FIG. 2 shows the structure of the stereoretentive ruthenium complex 1-Ru1a according to the present invention, obtained from X-ray structural analysis, in two spatial projections. [Diagram 2] FIG. 2 shows the structure of the stereoretentive ruthenium complex 1-Ru1ar according to the present invention in two space projections, obtained from X-ray structural analysis. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0048] The terms used herein have the following meanings. Terms not defined herein have the meanings given and understood by those skilled in the art in light of their best knowledge, the context of this disclosure and this patent application specification. Unless otherwise stated, the following chemical terminology conventions are used herein and have the meanings indicated as defined below.

[0049] As used herein, the term "halogen" means an element selected from F, Cl, Br, I.

[0050] The term "carbene" refers to an electrically neutral molecule in which a carbon atom has two non-bonding electrons in the singlet or triplet state and is bonded to two groups by one covalent bond or to one group by a double covalent bond. The term "carbene" also includes carbene analogs in which the carbene carbon atom is replaced by another chemical element, such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium, or tellurium.

[0051] The term "alkyl" refers to a saturated, linear or branched hydrocarbon substituent having the indicated number of carbon atoms. Examples of alkyl substituents are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n-decyl. Representative branched -(C1-C 10 ) Examples of alkyl include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1,3-dimethyl butyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -5-methylhexyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, and -3,3-dimethylheptyl.

[0052] The term "alkoxy" means an alkyl group as defined above attached through an oxygen bridge.

[0053] The term "perfluoroalkyl" means an alkyl group as defined above where all hydrogens have been replaced with the same or different halogens.

[0054] The term "cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of cycloalkyl substituents include -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.

[0055] The term "alkenyl" refers to an unsaturated, linear or branched, acyclic hydrocarbon substituent containing at least one carbon-carbon double bond having the indicated number of carbon atoms. Examples of alkenyl substituents include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl, and the like.

[0056] The term "cycloalkenyl" refers to an unsaturated cyclic or branched cyclic hydrocarbon substituent having the indicated number of carbon atoms and containing at least one carbon-carbon double bond. Examples of cycloalkenyl substituents are -cyclopropene, -cyclobutene, -cyclopentene, -cyclohexene, -cycloheptene, -cyclooctene, cyclononene, -cyclodecene, -methylcyclopropene, -ethylcyclobutene, -isopropylcyclopentene, -methylcyclohexene, and the like.

[0057] The term "aryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of aryl substituents include -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl, and the like.

[0058] The term "aralkyl" refers to an alkyl substituent as defined above substituted with at least one aryl as defined above. Examples of aralkyl substituents are -benzyl, -diphenylmethyl, -triphenylmethyl, and the like.

[0059] The term "heteroaryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms, in which at least one carbon atom is replaced with a heteroatom selected from O, N, and S. Examples of heteroaryl substituents include -furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.

[0060] The term "heterocycle" means a saturated, unsaturated or partially unsaturated, monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms, in which at least one carbon atom is replaced with a heteroatom selected from O, N and S. Examples of heterocyclic substituents include -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, -isoxazolyl, -pyrazolyl, -isothiazolyl, -triazinyl, -pyrrolidinonyl, -pyrrolidinyl, -hydantoinyl, -oxiranyl, -oxetanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumarinyl, -indolyl, -indolizinyl, -benzo[b]furanyl, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinolisinyl, -isoquinolyl, -quinolyl, -phthalazinyl, -naphthyridinyl, -carbazolyl, -β-carbolinyl, and the like.

[0061] The term "neutral ligand" refers to an uncharged substituent capable of coordinating with a metal center (transition metal atom). Examples of such ligands include N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbenes (CAACs), amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinatively unsaturated or aromatic hydrocarbons, alkyl and aryl halides, nitriles, isonitriles, sulfides, sulfoxides, sulfones, thioketones, thioamides, thioesters, thionoesters, and dithioesters.

[0062] The term "anionic ligand" refers to a substituent having a charge that can coordinate with a metal center (transition metal atom) and can partially or completely compensate for the charge of the metal center. Examples of such ligands include fluoride anions, chloride anions, bromide anions, iodide anions, cyanide anions, cyanate anions, thiocyanate anions, carboxylate anions, alcohol anions, phenol anions, thiol anions, thiophenol anions, hydrocarbon anions with delocalized charges (such as cyclopentadiene anion), anions of (organic) sulfates and (organic) phosphoric acids and their esters (e.g., anions of alkyl and aryl sulfonic acids, anions of alkyl and aryl phosphoric acids, anions of alkyl and aryl esters of sulfates, anions of alkyl and aryl esters of phosphoric acids, anions of alkyl and aryl esters of alkyl and aryl phosphoric acids, etc.). Alternatively, anionic ligands can be L linked as catechol anions, acetylacetone anions, salicylaldehyde anions, etc. 1 , L 2 and L 3 The anionic ligand (X 1 , X 2 ) and neutral ligands (L 1 , L 2 , L 3 ) can be linked to form a multidentate ligand, such as a bidentate ligand (X 1 -X 2), tridentate ligand (X 1 -X 2 -L 1 ), tetradentate ligand (X 1 -X 2 -L 1 -L 2 ), bidentate ligand (X 1 -L 1 ), tridentate ligand (X 1 -L 1 -L 2 ), tetradentate ligand (X 1 -L 1 -L 2 -L 3 ), bidentate ligand (L 1 -L 2 ), tridentate ligand (L 1 -L 2 -L 3 ) can also be formed. Examples of such ligands include catechol anion, dithiocatechol anion, acetylacetone anion, and salicylaldehyde anion.

[0063] The term "heteroatom" means an atom selected from the group including oxygen, sulfur, nitrogen, phosphorus, boron, silicon, arsenic, selenium, and tellurium.

[0064] The term "PAO" means polyolefin, an abbreviation for poly-alpha-olefin, which in the present case is an abbreviation used for low molecular weight polyolefins used as high boilers, and refers to a family of solvents and / or lubricants used herein as heat resistant, non-polar, high boilers that are the polymerization products of ethylene derivatives to form branched, saturated hydrocarbons. EXAMPLES

[0065] The following examples are included solely to illustrate and clarify certain aspects of the invention, and are not intended to limit the invention and should not be construed as limiting the full scope of the invention as defined in the appended claims. In the following examples, unless otherwise noted, standard materials and methods used in the art were applied, or manufacturer's recommendations for particular reactants and methods were followed.

[0066] Where necessary, model compounds for metathesis reactions were purified by fractional distillation and then stored under an inert gas atmosphere over activated inert aluminum oxide. Tetrahydrofuran was purified by distillation over sodium-potassium alloy in the presence of benzophenone and stored over 4 Å molecular sieves. Where appropriate, selected reactions were carried out under an argon atmosphere with the reaction vessel heated to 130 °C.

[0067] The starting compounds for the synthesis of the zinc complexes were commercially available.

[0068] The composition of the reaction mixture of the metathesis reaction was determined by gas chromatography using a PerkinElmer Clarus 680 GC equipped with a GL Sciences InertCap® 5MS / NP capillary column.

[0069] Individual components of the reaction mixture were identified by comparison of retention times with commercially available standards or were isolated from the reaction mixture whose structures were confirmed by NMR.

[0070] Example I Synthesis of new dithiolate ligands and the corresponding metal salts. Scheme 1 below illustrates the synthesis of dithiolate ligand precursors and compounds (general formulae VI and VII) that allow the preparation of stereoretentive ruthenium catalysts (general formulae 1-Ru1a-1-Ru1ar and 1-Ru2a-1-Ru2c, Scheme 10) that are the subject of the present invention. [ka]

[0071] Reactions R1-R4 shown in Scheme 1 were carried out using commercially available substrates based on procedures described in the literature with modifications developed by the authors. Unless otherwise specified, reactions used commercially available solvents as indicated and no attention was paid to the presence of oxygen and / or moisture.

[0072] Subsequent transformations described in Scheme 1 are shown below.

[0073] Reaction R1 In step R1 (scheme 1), the synthesis of diamides of general formula II is carried out. For this purpose, diamines of general formula I and dicarbonyl compounds, preferably oxalic acid, dimethyl oxalate or oxalyl chloride, are used. The conversion is carried out in water or in an organic solvent with a catalytic amount of an organic or inorganic acid or with an equivalent amount of a base, preferably a non-nucleophilic base. The product is isolated from the reaction mixture by filtration. [(i) J. Lin, P. Wang, Z. Zhang, G. Xue, D. Zha, J. Wang, X. Xu, Z. Li, Synth.Commun. 2020, 50, 823-830; (ii) OO Ajani, CA Obafemi, CO Ikpo, KO Ogunniran, OC Nwinyi, Chem. Heterocycl. Compd. 2009, 45, 1370-1378].

[0074] Example of reaction R1: [ka] O-phenylenediamine (2.0 g, 18.4 mmol), oxalic acid dihydrate (1.66 g, 18.4 mmol), 15 mL of water and a catalytic amount of paratoluenesulfonic acid (pTsOH) were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor (MW) and the contents of the vessel were heated for 10 min, maintaining a constant temperature of 100 °C. After the mixture was cooled to room temperature, the red crystals of the product obtained were filtered off, washed successively with small amounts of ethanol and diethyl ether and dried in air to give the expected product in 80% yield (2.4 g, 14.8 mmol). 1H NMR (400 MHz, DMSO-d6) δ=11.90 (brs, 2H), 7.07 (ddt, J = 18.1, 5.6, 3.5 Hz, 4H). 13 C NMR (101 MHz, DMSO-d6) δ=155.6, 126.0, 123.4, 115.6.

[0075] b. Reaction R2 In step R2 (Scheme 1), the obtained diamide of general formula II is converted to a 2,3-dichloroquinoxaline derivative of general formula III using a dehydrating chlorinating agent, preferably phosphoryl chloride or thionyl chloride. The reaction is carried out in an organic solvent or without a solvent, preferably in the presence of dimethylformamide. The reaction mixture is heated under a reflux condenser or in a microwave reactor. The product is isolated by precipitation followed by filtration of the resulting precipitate or by extraction with an organic solvent [R. Beldi, KF Atta, S. Aboul-Ela, ESH El Ashry, J. Heterocycl. Chem. 2011, 48, 50-56].

[0076] Example of reaction R2: [ka] The corresponding reaction product R1 (2.4 g, 14.8 mmol), POCl3 (5.5 mL, 59.2 mmol) and 15 mL of dry dimethylformamide were introduced into a reaction vessel equipped with a stirring element. The reaction mixture was heated in a microwave reactor for 20 min, keeping the temperature constant at 50 °C. After the reaction mixture was cooled to room temperature, the contents of the vessel were carefully poured onto ice. The colorless precipitate thus obtained was filtered and washed successively with ethanol and diethyl ether. As a result, the expected product was obtained as a colorless solid in 71% yield (2.1 g, 10.6 mmol). 1 H NMR (400 MHz, CDCl3) δ=8.03 (dd, J=6.4, 3.4 Hz, 2H), 7.81 (dd, J=6.4, 3.4 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ=145.4, 140.6, 131.3, 128.2.

[0077] c. Functionalization of the substituents to form carboxylic or sulfonic acid chlorides R a ~R d When one of the substituents in (Scheme 1) contains a functional group that reacts with thionyl chloride or phosphoryl chloride (e.g., carboxylic acid, sulfonic acid), the general formula: [ka] The compound of formula (1) is obtained.

[0078] These compounds can be used in addition reactions with nucleophiles in the presence or absence of a base to form ester:acyl or sulfone or amide:acyl or sulfone according to Scheme 4. [ka]

[0079] Example reactions: [ka] Dimethylamine hydrochloride (206 mg, 2.52 mmol), 2,3-dichloroquinoxaline-6-sulfonyl chloride (750 mg, 2.52 mmol) and 25 mL of dichloromethane were introduced into the reaction vessel. The vessel was placed in an acetone / dry ice cooling bath and triethylamine (0.7 mL, 5.04 mmol) was added dropwise to the reaction mixture. The vessel was then allowed to warm slowly overnight using the temperature inertia of the cooling bath. The next day, the reaction mixture was transferred to a separatory funnel and washed with water. The aqueous phase was extracted with two portions of dichloromethane. The combined organic phase was dried over anhydrous sodium sulfate and concentrated to about 10% of the initial volume, and then the product was precipitated by the addition of n-hexane. The resulting precipitate was filtered under reduced pressure and dried to give the product as a yellow solid in 65% yield (0.5 g, 1.63 mmol). 1 H NMR (400 MHz, chloroform-d) δ 8.49 (dd, J = 2.0, 0.6 Hz, 1H), 8.22-8.17 (m, 1H), 8.14-8.10 (m, 1H), 2.81 (s, 6H).

[0080] d. Reaction R3 In step R3 (Scheme 1), the derivative of general formula III obtained in the previous step is reacted with an alcoholic thiourea solution. The reaction is carried out at elevated temperature, preferably at 40-80 ° C. Depending on the water content in the solvent and the substrate used in the reaction, a mixture of products of general formula IVa and IVb in different proportions is obtained, which can be used for further reactions without significant influence on the yield. In the example shown, the main compound was that of general formula IVa. [(iii) R. Beldi, KF Atta, S. Aboul-Ela, ESH El Ashry, J. Heterocycl. Chem. 2011, 48, 50-56; (iv) Ya. Z. Voloshin, AS Belov, A. Yu. Lebedev, OA Varzatskii, M. Yu. Antipin, ZA Starikova, TE Kron, Russ. Chem. Bull. 2004, 53, 1218-1222]. The reaction product is isolated and purified by filtration.

[0081] Example of reaction R3: [ka] 2,3-Dichloroquinoxaline (10.3 g, 52 mmol) and thiourea (8.7 g, 115 mmol) were introduced into a reaction vessel equipped with a stirring element. The contents of the vessel were suspended in 120 mL of ethanol and then heated under a reflux condenser for 6 h. After completion of the reaction, the resulting suspension was cooled to room temperature, then filtered and washed with a small amount of ethanol and diethyl ether. After drying, the product was obtained as a yellow solid (11.0 g, 31.72 mmol) in 61% yield. 1 H NMR (400 MHz, DMSO-d6) δ 15.14 (brs, 1H), 9.97 (brs, 2H), 9.83 (brs, 2H), 7.88 (dt, J = 8.0, 1.0 Hz, 1H), 7.70-7.63 (m, 2H), 7.51 (ddd, J = 8.4, 5.6, 2.9 Hz, 1H). 13 C NMR (101 MHz, DMSO-d6) δ 171.0, 164.9, 160.3, 135.1, 131.6, 131.5, 128.2, 127.0, 117.0.

[0082] e. Reaction R4 In step R4 (Scheme 1), the derivative of general formula III is treated with sodium hydrogen sulfide in water or an organic solvent, preferably ethanol, at elevated temperature or in a microwave reactor [(v) S. Henfling, R. Kempt, J. Klose, A. Kuc, B. Kersting, H. Krautscheid, Inorg. Chem. 2020, 59, 16441-16453]. The product after the reaction is isolated by filtration.

[0083] Alternatively, the derivative of general formula III is treated with thiourea in water or an organic solvent, preferably ethanol, at elevated temperature or in a microwave reactor, then hydrolysis of the resulting mixture under aqueous conditions is carried out first with a solution of an alkali, preferably sodium hydroxide, and then with a solution of an organic or inorganic acid, preferably acetic acid.

[0084] Example of reaction R4: [ka] 1,2-Dichloropyrazine (2.0 g, 13.2 mmol), sodium hydrogen sulfide hydrate (2.95 g, 52.6 mmol) and 15 mL of water were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor and the contents were heated for 25 minutes, maintaining the temperature at 95° C. After cooling the reaction mixture to room temperature, the precipitate formed was filtered off, washed with a small amount of water, ethanol and diethyl ether, then dried to give the expected product in the form of purple crystals with a yield of 84% (1.6 g, 11.1 mmol). 1 H NMR (400 MHz, DMSO-d6) δ =13.72 (s, 2H), 6.87 (s, 2H). 13 C NMR (101 MHz, DMSO-d6) δ = 180.5, 118.0.

[0085] Alternative examples for reaction R4: [ka] 1,2-Dichloroquinoxaline (2.1 g, 10.6 mmol), thiourea (2.1 g, 27.4 mmol) and 15 mL of water were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor and the contents of the vessel were heated for 10 minutes, maintaining the temperature at 100° C. After the reaction mixture was cooled to room temperature, an aqueous NaOH solution (4.22 g in 30 mL of water) was added. The contents of the flask were stirred for another 10 minutes, after which 9.1 mL of glacial acetic acid was added. The precipitate was filtered, washed with water, ethanol and diethyl ether, and then dried. As a result, the expected product was obtained as a brown solid in 73% yield (1.5 g, 7.72 mmol). 1 H NMR (400 MHz, DMSO-d6) δ = 14.25 (s, 2H), 7.45-7.35 (m, 2H), 7.32-7.21 (m, 2H). 13C NMR (101 MHz, DMSO-d6) δ = 179.7, 128.3, 126.0, 116.0.

[0086] f. Reactions R5 and R6 Compounds of general formula IVa, IVb and V can be directly converted to compounds of general formula VI using similar reaction conditions. Each of these compounds (IVa, IVb and V) is treated with a metal complex, preferably zinc acetate or zinc chloride, in the presence of ethylenediamine in water or an organic solvent. The reaction products are separated by filtration.

[0087] Example of reaction R5: [ka] The isothiourethane salt (5.6 g, 15.9 mmol), zinc acetate dihydrate (7.0 g, 31.9 mmol), ethylenediamine (6.5 mL, 95.7 mmol) and 100 mL of water were introduced into a reaction vessel equipped with a stirring element. After 2 hours of reaction at room temperature, the yellow precipitate formed was filtered off, washed with water, ethanol and diethyl ether and dried. The expected product was obtained in 66% yield (4.5 g, 14.2 mmol).

[0088] By reaction R5 using zinc acetate(II), or iron(II) chloride, or copper(II) chloride, respectively, the following compounds having the general formula [ka] was generated.

[0089] Example of reaction R6: [ka] Zinc acetate dihydrate (1.19 g, 5.4 mmol), ethylenediamine (1.46 mL, 21.6 mmol), 1,2-dithioquinoxaline (0.7 g, 3.6 mmol) and 10 mL of isopropanol were introduced into a reaction vessel equipped with a stirring element. After 24 hours of reaction at room temperature, the yellow precipitate formed was filtered off, washed with water, ethanol and diethyl ether and dried to give the expected product 3-Zn1 in 75% yield (0.7 g, 2.72 mmol).

[0090] Reaction R6 gave the following list of compounds of general formula VI: [ka]

[0091] The zinc complexes 3-Zn1 to 3-Zn13 were characterized by ATR IR. The most characteristic absorption bands are shown below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0092] f. Example of reaction R7 In step R7 (Scheme 1), the derivative of general formula V is treated with one or more salts, or organometallic compounds, or metal hydrides, preferably lithium, sodium, potassium, magnesium, calcium or copper, respectively, in an organic solvent, preferably THF, at room temperature. The product VII does not need to be isolated and can be used directly for the synthesis of suitable catalysts (Example IV). Reaction R7 produced the following compounds with general formula VII: [ka]

[0093] Example II A general method for the synthesis of stereoretentive ruthenium complexes 1-Ru1a-1-Ru1ar and 1-Ru2a-1-Ru2c The synthesis of the stereoretentive ruthenium complexes that are the subject of the present invention consists of mixing, according to scheme 10, a metal complex of general structure VI, or a reaction R7 product of general formula VII, formed by reacting a compound of general formula V in situ with a source of metal cation as described above and optionally with a neutral ligand, with an alkylidene ruthenium complex of general structure 4, 4a-Ru or 4b-Ru. The reaction is carried out at room temperature or at elevated temperature, in an organic solvent, preferably tetrahydrofuran, while maintaining anhydrous and anaerobic conditions. The product is isolated by filtering the reaction mixture and evaporating the filtrate obtained, to obtain the expected product 1-Ru1a-1-Ru1ar or 1-Ru2a-1-Ru2c according to scheme 10. [ka]

[0094] Example III Preparation of stereoretentive ruthenium complexes using 3-Zn1 ligand The transformations described below were carried out under an inert gas atmosphere, using a glove box and / or vacuum argon line where necessary, and with deoxygenated and anhydrous reactants and solvents. [ka]

[0095] Hoveyda-Grubbs second generation complex (50.0 mg, 0.07 mol), quinoxalino-2,3-dithiolate zinc 3-Zn1 complex (33.5 mg, 0.14 mmol), and 5 mL of tetrahydrofuran were introduced into a 10 mL vial equipped with a stirring element. The contents of the vial were stirred at room temperature for 8 hours and the solvent was evaporated. The residue was suspended in dichloromethane and filtered, preferably through a syringe filter or a Celite pad. After evaporation of the solvent, the product 1-Ru1a was obtained as a solid in 95% yield (0.067 mmol, 55.8 mg).

[0096] Example IV Preparation of stereoretentive ruthenium complexes using the 3-K1 ligand (obtained from reaction R7, Scheme 1) The transformations described below were carried out under an inert gas atmosphere, using a glove box and / or vacuum argon line where necessary, and with deoxygenated and anhydrous reactants and solvents. [ka]

[0097] Quinoxalino-2,3-dithione (18.6 mg, 0.096 mmol), KHMDS (38.2 mg, 0.196 mmol) and 5 mL of THF were introduced into a 10 mL vial equipped with a stirring element. After stirring the contents of the vial for 2 h, Hoveyda-Grubbs second generation complex (Hov-II, 30.0 mg, 0.048 mmol) was added and the mixture was stirred for another 22 h, after which the solvent was evaporated. The residue was suspended in dichloromethane and filtered, preferably through a syringe filter or a Celite pad. The filtrate was concentrated to about 2 mL, and then 15 mL of hexane was added slowly. The formed crystals were collected and washed with a small amount of hexane. After removal of the residual solvent, the solid 1-Ru1b product was obtained in 70% yield (0.033 mmol, 25.0 mg).

[0098] Using the methods described in Examples III and IV, a series of complexes 1-Ru1a to 1-Ru1ar or 1-Ru2a to 1-Ru2c were obtained, the structures of which are shown below.

[0099] [ka] JPEG2025504619000059.jpg190152 JPEG2025504619000060.jpg240152

[0100] All the above complexes were characterized using nuclear magnetic resonance spectroscopy. Table 1 shows the cation exchange ratios in the selected solvents. 1 The benzylidene proton shifts of each complex in the H NMR spectrum are summarized.

[0101] [Table 1] JPEG2025504619000062.jpg235164 JPEG2025504619000063.jpg222164 JPEG2025504619000064.jpg207164 JPEG2025504619000065.jpg235164 JPEG2025504619000066.jpg214164 JPEG2025504619000067.jpg225164 JPEG2025504619000068.jpg70164

[0102] Example V Applications of new stereoretentive ruthenium complexes. In the application examples of the new stereoretentive metathesis catalysts, the following reference ruthenium catalysts 1-Ru0a, 1-Ru0b, 1-Ru0c and reference molybdenum catalysts Mo1, Mo2, Mo3 were also used for comparison. For some results, reference values ​​from the literature are given. The %Z and %E values ​​indicate the percentage of the given isomer relative to both isomers present in the product. Unless otherwise stated, all operations were carried out under an inert gas atmosphere, using anhydrous and deoxygenated solvents and reagents. Gas chromatographic analysis was carried out using the internal standard method. [ka]

[0103] Example VI Activity study of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of methyl oleate (OM) A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, and a solution of 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m, 1-Ru1n, 1-Ru1x catalysts (0.001 equiv.) in THF were introduced into a vial equipped with a stirring element such that the concentration of methyl oleate in the mixture was 0.1 M. The reaction was carried out at room temperature (RT) for 18 h. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 2. In the table, "OM" is methyl oleate, "9-ODE" is octadec-9-ene, and "9-OKD" in this example is dimethyl octadec-9-enodiate. [ka]

[0104] [Table 2]

[0105] Example VII Study of the activity of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of methyl oleate (OM) at elevated temperatures A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, and a solution of 1-Ru1a, 1-Ru1c, 1-Ru1n, 1-Ru1x catalysts (0.0001 equiv.) in THF were introduced into a vial equipped with a stirring element such that the concentration of methyl oleate in the mixture was 0.1 M. The reaction was carried out at 60 °C for 18 h. The conversion and composition of the mixture were determined by gas chromatography. The reaction results are shown in Table 3. In the table, "OM" is methyl oleate, "9-ODE" is octadec-9-ene, and "9-OKD" is dimethyl octadec-9-enodiate. [ka]

[0106] [Table 3]

[0107] Example VIII Study of the effect of the addition of zinc derivatives and other metals on the activity and selectivity of a novel stereoretentive ruthenium complex in the cross-metathesis reaction of methyl oleate (OM) A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, a solution of the catalyst 1-Ru1c (0.0002 equiv.) in THF and a solution of 3-Zn1 (0.0-1.0 equiv.) were introduced into a vial equipped with a stirring element so that the concentration of methyl oleate in the reaction mixture was 0.1 M. The reaction was carried out at 60 ° C for 18 h. The conversion and composition of the mixture were determined by gas chromatography. The reaction results are shown in Table 4. In the table, "OM" is methyl oleate, "9-ODE" is octadec-9-ene, and "9-OKD" is dimethyl octadec-9-enodiate. [ka]

[0108] [Table 4]

[0109] Example IX Activity study of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of allylbenzene with (Z)-1,4-diacetoxybut-2-ene A solution of allylbenzene (1.0 eq.) in THF, a solution of (Z)-1,4-diacetoxybut-2-ene (2.0 eq.) in THF, a solution of tetradecane (0.1 eq.) in THF, a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.05 eq.) in THF were introduced into a vial equipped with a stirring element such that the allylbenzene concentration in the mixture was 0.237 M. The reaction was carried out at room temperature for 4 hours. The conversion and composition of the mixture were determined by gas chromatography. The reaction results are shown in Table 5. [ka]

[0110] [Table 5]

[0111] Example X Activity study of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of allylbenzene with (Z)-but-2-ene-1,4-diol Solutions of allylbenzene (1.0 equiv.) in THF, (Z)-but-2-ene-1,4-diol (2.0 equiv.) in THF, tetradecane (0.1 equiv.) in THF, catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.05 equiv.) in THF were introduced into a vial equipped with a stirring element such that the concentration of allylbenzene in the mixture was 0.237 M. The reaction was carried out at room temperature for 4 h. The conversion and composition of the mixture were determined by gas chromatography (GC). The results of the model reactions are summarized in Table 6. [ka]

[0112] [Table 6]

[0113] Example XI Activity study of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of methyl elaidate (EM) A solution of methyl elaidate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, and a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.075 equiv.) in THF were introduced into a vial equipped with a stirring element such that the concentration of methyl elaidate in the mixture was 0.42 M. The reaction was carried out at room temperature for 20 h. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 7. In the table, "EM" is methyl elaidate, "9-ODE" is octadec-9-ene, and "9-OKD" is dimethyl 9-octadecenedioate. [ka]

[0114] [Table 7]

[0115] Example XII Activity study of novel stereoretentive ruthenium complexes in the cross metathesis reaction of dec-9-en-1-ol acetate with (Z)-hex-3-ene. Synthesis of (Z)-dodec-9-en-1-ol acetate, the insect sex pheromone of the moth, Eupoecilia ambiguella Solutions of dec-9-en-1-ol (1.0 eq.) in THF, (Z)-hex-3-ene (2.0 eq.) in THF, tetradecane (0.1 eq.) in THF, catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m, 1-Ru1t or 1-Ru1x (0.05 eq.) in THF were introduced into a vial equipped with a stirring element such that the concentration of dec-9-en-1-ol in the mixture was 0.237 M. The reaction was carried out at room temperature for 20 h. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 8. [ka]

[0116] [Table 8]

[0117] Example XIII Activity study of novel stereoretentive ruthenium complexes in the ring-closing metathesis reaction of (Z)-6-nonenyl oleate (Z)-6-nonenyl oleate (1.0 equiv.), 2.5 mL PAO6, and an appropriate amount of catalyst 1-Ru1a or 1-Ru0a were introduced into a reaction vessel equipped with a stirring element. The vessel was fitted with a Hickman distillation adapter, which was then connected to a diffusion pump (nominal pressure 1×10 -6The mixture was placed in a heating bath at 110° C. (bar). The reaction was carried out for 8 hours at 110° C. After the reaction was completed, the distillate was purified by column chromatography (SiO2, n-hexane followed by ethyl acetate as eluent). As a result, a pure product was obtained and the Z-isomer content was determined by gas chromatography. The results of the model reaction are shown in Table 9. [ka]

[0118] [Table 9]

[0119] Example XIV Activity study of novel stereoretentive ruthenium complexes in the ring-closing metathesis (RCM) reaction to obtain civetone The substrate (1.0 equiv.), 2.5 mL PAO6, and an appropriate amount of catalyst 1-Ru1a or 1-Ru0a were introduced into a reaction vessel equipped with a stirring element. The vessel was fitted with a Hickman distillation adapter, which was then connected to a diffusion pump (nominal pressure 1×10 -6 The mixture was placed in a heating bath at 110° C. (mbar). The reaction was carried out at 110° C. for 8 hours. After the reaction was completed, the distillate was purified by column chromatography (SiO2, using n-hexane followed by ethyl acetate as eluent). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained and the Z-isomer content was determined by gas chromatography. The results of the model reaction are shown in Table 10. [ka]

[0120] [Table 10]

[0121] The results shown in Examples XIII and XIV show that 1-Ru0a, representative of a stereoretentive thiocatechol complex, does not give satisfactory results in the synthesis of macrocyclic lactones and ketones at elevated temperatures, whereas the complexes that are the subject of the present invention show much higher stereoselectivities and / or yields under the same conditions.

[0122] Example XV Study on the activity of Z-selective molybdenum complexes in the ring-closing metathesis reaction of (Z)-6-nonenyl oleate The substrate (1.0 equiv.), 2.5 mL of PAO6, and catalyst Mo1, Mo2, or Mo3 in tablet form were introduced into the reaction vessel. The vessel was fitted with a Hickman distillation adapter and then a diffusion pump (nominal pressure 1 × 10 -6 The reaction was connected to a 300 psi (1000 psi) kettle (1000 psi) and placed in a heating bath. The reaction was carried out at 110° C. for 8 h. After the reaction was complete, the distillate was purified by column chromatography (SiO2, using n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained and the content of Z-isomer was determined by gas chromatography. The results of the model reaction are shown in Table 11. [ka]

[0123] [Table 11]

[0124] As expected, the non-stereoselective Mo1 complex showed an E / Z ratio typical of standard molybdenum complexes. In contrast, the Z-selective Mo2 complex unexpectedly did not show the expected Z-selectivity. Similarly, no excess of the Z-isomer was obtained with the Z-selective Mo3 complex, another representative of the technology. The above results show that the cited method for the synthesis of macrocyclic lactones at elevated temperatures is incompatible with the Z-selective alkylidene molybdenum complexes representative of the standard technology, but that the complexes that are the subject of the present invention show high stereoselectivity under the same conditions.

[0125] Example XVI Study on the activity of Z-selective ruthenium complexes in the ring-closing metathesis reaction of (Z)-6-nonenyl oleate The substrate (1.0 equiv.), 2.5 mL of PAO6, and the catalyst were introduced into the reaction vessel. The vessel was fitted with a Hickman distillation adapter and then heated with a diffusion pump (nominal pressure 1 × 10 -6 The flask was connected to a 300 psi (1000 psi) aeration tube (1000 psi, ... [ka]

[0126] [Table 12]

[0127] The results presented in Example XVI show that Z-selective 1-Ru0c complexes, representative of the state of the art, do not provide satisfactory results in the synthesis of macrocyclic lactones at elevated temperatures.

[0128] Example XV Study on the activity of novel stereoretentive ruthenium complexes in the synthesis of macrocyclic compounds via ring-closing metathesis (RCM) reactions The substrate (1.0 equiv.), 2.5 mL PAO6, and the corresponding amount of 1-Ru1a catalyst were introduced into the reaction vessel. The vessel was fitted with a Hickman distillation adapter and then heated with a diffusion pump (nominal pressure of 1 × 10 -6 The reaction was connected to a 300 rpm, 100 rpm (300 rpm) and placed in a heating bath. The reaction was carried out at 110° C. for 8 hours. After the reaction was complete, the distillate was purified by column chromatography (SiO2, using n-hexane followed by ethyl acetate as eluent). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained and the content of Z-isomer was determined by gas chromatography. The results of the model reaction are shown in Table 12. A Hickman distillation adapter was attached and a diffusion pump (nominal pressure 1x10 -6 The reaction was performed at 110° C. for 8 h. After completion of the reaction, the distillate was purified by column chromatography (SiO2, n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the Z-isomer content was determined by gas chromatography. The result of the model reaction is shown in Scheme 24. [ka]

[0129] Example XVI Activity study of novel stereoretentive ruthenium complexes in the cross-metathesis reaction of Z-configured terminal or internal olefins with Z-configured internal symmetric olefins A solution of Z-configured terminal or internal olefin (1.0 equiv.) in THF and a solution of Z-configured symmetric internal olefin (2.0 equiv.) in THF were introduced into a vial equipped with a stirring element such that the concentration of terminal olefin in the mixture was 0.2 M. A solution of 1-Ru0a, 1-Ru1a (0.02 equiv.) catalyst in THF was added to the mixture or a solution of 1-Ru0a, 1-Ru1a (0.04 equiv.) catalyst in THF was added in two portions (the second portion was added 1 h after the start of the reaction). The reaction was carried out at room temperature for 2 h. The composition of the mixture was determined by NMR spectroscopy. The results of the model reaction are shown in Scheme 25.

[0130] [ka]

[0131] [Literature] TIFF2025504619000094.tif62164

Claims

1. Ruthenium complexes of formula 1-Ru. 【Chemistry 1】 (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC), or a phosphine; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl, C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form quaternary ammonium, tertiary sulfonium, or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; R 13 and R 14 are independently hydrogen, halogen, optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Cycloalkynyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxy, optionally substituted C 6 -C 25 Aralkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxy, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents taken together are C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 may form a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium or phosphorus, which may be selected from the group consisting of hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkenes, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxy, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxy, C 5 -C 25 Optionally substituted with one and / or more substituents independently selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; G is, -L 2 Coordinate 【Chemistry 2】 In the formula, R 20 and R 21 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl group, C 5 -C 25 aralkyl groups, which are independently hydrogen, halogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 5 -C 20 Heteroaryl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 Heteroaryloxy, alkoxy (-OR"), sulfide (-SR"), amine (-NR") 2 ) groups, wherein the R″ groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Let's join together and 5 -C 25 Forming a ring; Each R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy group, hydroxymethyl group (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group, where each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-COR d ) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; and amine groups (-NR c 2 ), methylamine group (-CHNR c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amine groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently selected from the group consisting of C 1 -C 25 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Forming a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or - 1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, 3- to 12-membered heterocycle, acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups, where the R' groups are independently selected from the group 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 perfluoroaryl; 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, —CH 2 -, -CHR'-, or -CR' 2 - represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R" is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or -Heteroatom 2 methylidene optionally substituted with hydrogen, R′ substituents, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroaryl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR' 2 ), sulfonic acid group (-SO 2 R' is optionally substituted with a group selected from an acyl group (-COR'), a cyano group (-CN), a carboxyl group (-COOH), an ester group (-COOR'), an ester group (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups; 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, where R′ is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, (CH 2 )-, -(CHR')-, or (CR' 2 )-represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R" is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or - 3 heteroatoms halogen, and the dashed line indicates the heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 Perfluoroaryl .)

2. R 13 and R 14 The substituents are independently hydrogen, and / or independently hydrogen, halogen, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 C substituted with 5 -C 25 aryl, where the R groups are independently hydrogen, 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl, and the two R groups together are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 A heterocycloalkyl ring may be formed, optionally further comprising C 1 -C 12 or R" is a ketone group (-COR c ) (R c is C 1 -C 12 perfluoroalkyl) or an alkoxy group (—OR d ), where R d is C 1 -C 12 Alkyl or C containing nitrogen, oxygen or sulfur 3 -C 12 Heterocycloalkyl, optionally further represented by C 1 -C 12 2. The ruthenium complex of claim 1 which is substituted with an alkyl group.

3. A structure represented by the general formula in which the neutral L1 ligand is selected from 2a, 2b, 2c, or 2d. 【Chemistry 3】 (In the formula: R 20 and R 21 Each substituent is independently selected from the group consisting of 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl group, C 5 -C 25 Aralkyl groups, which are hydrogen, halogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 Heteroaryloxy, or halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, amino group (-NR") 2 wherein the R groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Together, they form Ring C. 5 -C 25 forming a group; Each R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy groups, hydroxymethyl groups (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group (wherein each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-COR d ) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; and amine groups (-NR c 2 ), methylamine group (-CHNR c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with any of C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amine groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; R 28 , R 29 , and R 30 The substituents are independently selected from the group consisting of C 1 -C 25 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Form a system.) The ruthenium complex according to claim 1 or 2, which has the formula:

4. The ruthenium complex according to any one of claims 1 to 3, represented by the formula 1a-Ru. 【Chemistry 4】 (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a phosphine; n′ is 1 or 0. Z is selected from the group including halogen, O, S, Se, or NR″ groups, where R″ is methylidene, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR' 2 ), sulfonic acid group (-SO 2 R'), a formyl group (-COH), where R' is 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, or halogen, and when Z is halogen, R 15 does not exist; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 Heteroaryloxy, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; R 15 are independently hydrogen, C 1 -C 25 Alkyl, C 1 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 24 Aryloxy, -COOR'" group, CH 2 COOR''' group, -CONR''' 2 group, -CH 2 C.O.N.R.' 2 group, -COR''' group, -CH 2 COR''' group, -CH 2 CON(OR''') (R''') group, -CH 2 CON(OR''')(R'') group, or halogen, where R''' is C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenyl, C 6 -C 20 aryl, which are each independently selected from at least one C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 6 -C 24 optionally substituted with aryloxy, or halogen; R 16 , R 17 , R 18 , and R 19 are independently hydrogen, halogen, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, C 5 -C 25 Aryl groups, alkoxy groups (-OR"), sulfide groups (-SR"), sulfoxide groups (-S(O)R"), sulfonium groups (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSRR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl, where R 16 , R 17 , R 18 , and R 19 The substituents taken together form a substituted or unsubstituted cyclic C 4 -C 10 or polycyclic C 4 -C 12 A system may be formed.)

5. A ruthenium complex according to any one of claims 1 to 3 having the formula 1b-Ru. 【Chemistry 5】 (In the formula: L 1 is an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a PR 3 is a neutral ligand selected from phosphines; L 2 are N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbenes (CAACs), and PRs. 3 a neutral ligand selected from a phosphine derivative or a pyridine derivative; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 R forms a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; 13 and R 14 are independently hydrogen, halogen, optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Cycloalkynyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxy, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxy, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents taken together are C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 may form a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium, or phosphorus, which may be selected from the group consisting of hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkenes, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxy, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxy, C 5 -C 25 may be independently substituted with one and / or more substituents selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycle.

6. A ruthenium complex according to any one of claims 1 to 5 having the formula 1b-Ru. 【Chemistry 6】 (In the formula, L 1 The ligand is 【Chemistry 7】 (In the formula: R 20 and R 21 Each substituent is independently selected from the group consisting of 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl group, C 5 -C 25 Aralkyl groups, which are hydrogen, halogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 Heteroaryloxy, or halogen, alkoxy group (-OR"), sulfide group (-SR"), halogen, amino group (-NR") 2 wherein the R groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Together, they form Ring C. 5 -C 25 forming a group; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy group, hydroxymethyl group (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group, where each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; amine groups (-NR c 2 ), methylamine group (-CH 2 N.R. c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, together, form C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally further comprising C 1 -C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amine groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; R 28 , R 29 , and R 30 The substituents are independently selected from the group consisting of C 1 -C 25 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , and R 30 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 (Forming a system) and In the ceremony, L 2 The ligand is 【Chemistry 8】 (In the formula, each R 20 and R 21 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy groups, or halogens, alkoxy groups (-OR"), sulfide groups (-SR"), halogens, amino groups (-NR") 2 wherein the R groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Together, they form Ring C. 5 -C 25 forming a group; Each R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy group, hydroxymethyl group (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group, where each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-COR d ) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; amine groups (-NR c 2 ), methylamine group (-CH 2 N.R. c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, together, form C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally further comprising C 1 -C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amine groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently hydrogen, halogen, C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; R 13 and R 14 are independently hydrogen, halogen, optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Cycloalkynyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxy, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxy, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents taken together are C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 may form a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium, or phosphorus, which may be selected from the group consisting of hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkenes, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxy, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxy, C 5 -C 25 perfluoroaryl, 3- to 12-membered heterocycle; It is.)

7. The structure is 【Chemistry 9】 【change】 【change】 The ruthenium complex according to any one of claims 1 to 6, characterized in that it is represented by a formula selected from the following:

8. A compound having a structure defined in formula 3a or 3b. 【Chemistry 10】 (In the formula, M is a monovalent or divalent metal cation; n is 0, 1, 2 or 3; E is a group, or multiple groups if the heteroatom is nitrogen or phosphorus: 1 -C 25 Alkyl group, C 1 -C 25 Cycloalkyl group, C 5 -C 20 Alkoxy group, C 5 -C 20 Aryl Group C 7 -C 20 Aralkyl group, C 5 -C 24 Aryloxy group, C 2 -C 12 Alkenyl group, C 6 -C 20 Heteroaryl group, C 5 -C 24 At least one heteroatom selected from the group including oxygen, sulfur, selenium, nitrogen, phosphorus, substituted with a heteroaryloxy group, or hydrogen, and these groups are preferably at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or when two identical or different heteroatoms constitute a chelating system, they together form a substituted or unsubstituted cyclic C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Forming a system, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 , polycyclic aromatic C 4 -C 10 , and polycyclic heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 Forming a ring, the ring may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus.

9. Compound 3c, 3d or 3e according to claim 8. 【Chemistry 11】 (In the formula, M 2+ are Zn, Cu, Mg, Ca cations, M + is Li, Na, K, Cs, Cu or Cu×(E) n is a cation, n is 1 or 2; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 , polycyclic aromatic C 4 -C 10 , and polycyclic heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, C 1 -C 25 Alkyl, C 1 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted with perfluoroalkyl, or two selected R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 The substituents taken together form a substituted or unsubstituted cyclic C 4 -C 10 , polycyclic C 4 -C 12 , heterocyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system: hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 and optionally substituted with one or more substituents selected from heteroaryloxy and halogen.

10. Compound 3f according to claim 8 or 9. 【Chemistry 12】 (In the formula, M 2+ is a Zn cation, R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 Forming a ring, the ring may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus.

11. The compound according to any one of claims 8 to 10, whose structure is represented by a formula selected from 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13, and 3-K1. 【Chemistry 13】

12. A ruthenium complex of formula 1-Ru according to any one of claims 1 to 6: 【Chemistry 14】 (In the formula: L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC), or a phosphine; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; R 13 and R 14 are independently hydrogen, halogen, optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Cycloalkynyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxy, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxy, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents taken together are C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 may form a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium or phosphorus, which may be selected from the group consisting of hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkenes, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxy, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxy, C 5 -C 25 may be independently substituted with one and / or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents are independently preferably hydrogen, and / or independently hydrogen, halogen, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 C substituted with 5 -C 25 aryl, where the R groups are independently hydrogen, 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl, and the two R groups together are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 A heterocycloalkyl ring may be formed, optionally further comprising C 1 -C 12 or R" is a ketone group (-COR c ) (R c is C 1 -C 12 perfluoroalkyl) or an alkoxy group (—OR d ) (R d is C 1 -C 12 Alkyl or C containing nitrogen, oxygen or sulfur 3 -C 12 heterocycloalkyl, optionally C 1 -C 12 substituted with an alkyl group; G is, -L 2 Coordinate 【Chemistry 15】 In the formula, R 20 and R 21 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl group, C 5 -C 25 Aralkyl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy groups, or halogens, alkoxy groups (-OR"), sulfide groups (-SR"), halogens, amine groups (-NR") 2 wherein the R groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Let's join together and 5 -C 25 Forming a ring; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy groups, hydroxymethyl groups (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group (wherein each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; amine groups (-NR c 2 ), methylamine group (-CH 2 N.R. c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, together, form C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally further comprising C 1 -C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amino groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently selected from the group consisting of C 1 -C 25 Alkyl, C 1 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Form a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or - 1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, 3- to 12-membered heterocycle, and acyl group (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups, where R' groups are 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 perfluoroaryl; 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, (CH 2 )-, -(CHR')-, or (CR' 2 )-represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or -Heteroatom 2 methylidene optionally substituted with hydrogen, R′ substituents, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroaryl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR' 2 ), sulfonic acid group (-SO 2 R' is optionally substituted with a group selected from acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups; 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, where R′ is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, (CH 2 )-, -(CHR')-, or (CR' 2 )-represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or - 3 heteroatoms halogen, and the dashed line indicates the heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 Perfluoroaryl (selected from A method for producing a ruthenium complex of the formula: Formula 4-Ru: 【Chemistry 16】 (In the formula: X 1 and X 2 are independently a halogen anion, -CN, -SCN, -OR a , -SR a , -O(C=O)R a , -O(SO 2 ) R a , and -OSi(R a ) 3 is an anionic ligand selected from the group comprising the group a is C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenyl or C 5 -C 20 Aryl, having at least one C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 optionally substituted with heteroaryloxy or halogen; L 1 is a neutral ligand selected from an N-heterocyclic carbene (NHC), a cyclic alkylaminocarbene (CAAC) or a phosphine; R 13 and R 14 are independently hydrogen, halogen, optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Optionally substituted C which is cycloalkynyl 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxy, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxy, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycle; Here, R 13 and R 14 The substituents taken together are C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 may form a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium or phosphorus containing 3-12 membered heterocycles, hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkenes, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxy, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxy, C 5 -C 25 optionally independently substituted with one and / or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; Here, R 13 and R 14 The substituents are independently preferably hydrogen and / or hydrogen, C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R ″) independently substituted C 5 -C 25 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; G is, -L 2 Coordinate 【Chemistry 17】 In the formula, R 20 and R 21 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group, or C 5 -C 20 Heteroaryl group, C 5 -C 25 Aralkyl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy groups, or halogens, alkoxy groups (-OR"), sulfide groups (-SR"), halogens, amine groups (-NR") 2 wherein the R groups are independently selected from the group consisting of hydrogen, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 aralkyl or R 20 and R 21 Let's join together and 5 -C 25 Forming a ring; Each R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents are independently hydrogen, halogen, hydroxyl group, C 1 -C 12 Alkoxy groups, hydroxymethyl groups (-CH 2 OH), amine group (-NR a 2 Optionally substituted C 1 -C 12 An alkyl group (wherein each R a are independently hydrogen or C 1 -C 12 alkyl or two R a The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C 3 -C 25 heterocycloalkyl), C 3 -C 12 Cycloalkyl group; C 5 -C 20 Aryl group, C 5 -C 20 Heteroaryl group, ester group (-OCOR b ), (-CORd) group, methyl ester group (-CH 2 O.C.O.R. b ), where R b is C 5 -C 20 Aryl group or C 5 -C 20 perfluoroaryl groups; amine groups (-NR c 2 ), methylamine group (-CH 2 N.R. c 2 ), where each R c are independently hydrogen or C 1 -C 12 alkyl or two R c The bases, together, form C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally further comprising C 1 -C 12 and wherein the heteroatoms present in the heterocycle are substituted with one or two C alkyl groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, Independently, hydroxyl (OH), C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, halogen, C 1 -C 12 C optionally substituted with an alkyl group 3 -C 12 Heterocycloalkyl, ester group (-COOR d ) or (-COR d ) group, where R d is C 5 -C 20 Aryl group or C 5 -C 20 Perfluoroaryl groups, or amino groups (-NR e 2 ), where each R d are independently hydrogen or C 1 -C 12 alkyl, and two R e The bases, taken together, are C 3 -C 12 Cycloalkyl ring or C containing nitrogen, oxygen or sulfur 3 -C 25 Heterocycloalkyl may be formed, optionally with C 1 -C 12 Further substituted with an alkyl group, wherein the heteroatoms present in the heterocycle are one or two C groups forming a primary, secondary or tertiary amine, or a quaternary ammonium, tertiary sulfonium or quaternary phosphonium group. 1 -C 12 may be substituted with an alkyl group, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 The substituents may be optionally linked to each other to form a cyclic C 4 -C 10 System or polycyclic C 4 -C 12 A system may be formed; Each R 28 , R 29 , and R 30 The substituents are independently selected from the group consisting of C 1 -C 25 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, which are heteroaryloxy groups having at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl or R 28 , R 29 , R 30 Together, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 A substituted or unsubstituted ring C which may be substituted with one and / or more substituents selected from heteroaryloxy and halogen; 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Forming a system; Each R 31 , R 32 , R 33 , R 34 and R 35 The substituents are independently selected from the group consisting of C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl groups, which are hydrogen, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 may be independently substituted with one and / or more substituents selected from the group including heteroaryloxy groups, or halogen; or - 1 heteroatom selected from the group containing oxygen, sulfur, and selenium; hydrogen, halogen, oxygen, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, 3- to 12-membered heterocycle, acyl (-COR'), cyano (-CN), carboxyl (-COOH), ester (-COOR'), ester (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), Weinreb amide (-CON(R')(OR')), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups, where R' groups are 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 perfluoroaryl; 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, or C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, —CH 2 )-, -CHR'-, or -CR' 2 - represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or -Heteroatom 2 methylidene optionally substituted with hydrogen, R′ substituents, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroaryl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, acyl group (-COR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (-CONR' 2 ), sulfonyl group (-SO 2 R' is optionally substituted with a group selected from an acyl group (-COR'), a cyano group (-CN), a carboxyl group (-COOH), an ester group (-COOR'), an ester group (-CH 2 COOR'), ester (-CHR'COOR'), ester (-C(R') 2 COOR'), amide (-CONR' 2 ), sulfonic acid (-SO 2 R'), formyl (-COH), sulfonamide (-SO 2 N.R. 2 ), ketones (-COR'), thioamides (-CSNR' 2 ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSR'), dithioester (-CS 2 R') groups; 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, where R′ is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, and the dashed line indicates the separation between the heteroatom and R 14 represents a direct bond to a substituent, or R 14 Between the substituent and the heteroatom, (CH 2 )-, -(CHR')-, or (CR' 2 )-represents a connection via a methylene bridge, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R" is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 is a perfluoroaryl; or - 3 heteroatoms halogen, and the dashed line indicates the heteroatom and R 14 represents a direct bond to a substituent, where R 14 The substituents are hydrogen, halogen, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxy, 3- to 12-membered heterocycle, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″) 5 -C 15 aryl, where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 Perfluoroaryl (selected from with an alkylidene ruthenium complex of formula 3a or 3b: 【Chemistry 18】 (In the formula, M is a monovalent or divalent metal cation; n is 0, 1 or 2; E is a group, or multiple groups if the heteroatom is nitrogen or phosphorus: 1 -C 25 Alkyl group, C 1 -C 25 Cycloalkyl group, C 5 -C 20 Alkoxy group, C 5 -C 20 Aryl Group C 7 -C 20 Aralkyl group, C 5 -C 24 Aryloxy group, C 2 -C 12 Alkenyl group, C 6 -C 20 Heteroaryl group, C 5 -C 24 At least one heteroatom selected from the group including oxygen, sulfur, selenium, nitrogen, phosphorus, substituted with a heteroaryloxy group, or hydrogen, and these groups are preferably at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or when two identical or different heteroatoms constitute a chelating system, they together form a substituted or unsubstituted cyclic C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 Forming a system, hydrogen, C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxy, C 5 -C 24 Aryloxy, C 5 -C 20 optionally substituted with one and / or more substituents selected from heteroaryloxy and halogen; R 1 and R 2 are independently hydrogen, halogen, C 1 -C 25 Alkyl, C 5 -C 20 Alkoxy, C 5 -C 20 Aryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxy, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 heteroaryloxy, which are at least one C 1 -C 12 Alkyl or C 1 -C 12 Optionally substituted by perfluoroalkyl, or R 1 and R 2 are independently an alkoxy group (-OR"), a sulfide group (-SR"), a sulfoxide group (-S(O)R"), a sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together are C 5 -C 25 Forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, and optionally further C 1 -C 12 The heterocycle may be substituted with one or two C alkyl groups. 1 -C 12 may be substituted with alkyl groups to form primary, secondary or tertiary amines, or quaternary ammonium, tertiary sulfonium or quaternary phosphonium groups; Or R 1 and R 2 together form a substituted or unsubstituted cyclic ring C 4 -C 10 , polycyclic C 4 -C 12 , aromatic C 4 -C 10 , heteroaromatic C 4 -C 10 , polycyclic aromatic C 4 -C 10 , and polycyclic heteroaromatic C 4 -C 10 These form the system, which consists of hydrogen, halogens, C 1 -C 25 Alkyl group, C 1 -C 12 Perfluoroalkyl Groups, C 1 -C 12 Alkoxy group, C 5 -C 24 Aryloxy group, C 5 -C 20 Heteroaryloxy group, C 2 -C 25 Alkenyl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R” 2 ), sulfonyl group (-SO 2 R″), sulfonamide group (—SO 2 N.R.” 2 ), amine group (-NR" 2 ), ammonium group (-N + R” 3 ), nitro group (-NO 2 ), cyano group (-CN), phosphonate group (-P(O)(OR") 2 ), phosphinate group (-P(O)R"(OR")), phosphonite group (-P(OR") 2 ), a phosphine group (-PR" 2 ), phosphine oxide group (-P(O)R" 2 ), a phosphonium group (-P + R” 3 ), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thioester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), where the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl or the two R groups together form C 5 -C 25 forming a ring, which may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, and phosphorus; with a compound having a structure defined by:

13. Use of a compound of formula 1-Ru according to any one of claims 1 to 7 as a precatalyst and / or catalyst in olefin metathesis reactions, in particular in ring-closing metathesis (RCM), cross metathesis (CM), homometathesis (cross metathesis between two molecules of the same olefin), ethenolysis, isomerization, diastereoselective ring rearrangement metathesis (DRRM) reactions, alkene-alkyne (ene-yne) metathesis or ROMP or ADMET type polymerization reactions.

14. The use according to claim 13, wherein the olefin metathesis reaction is carried out with the catalyst and / or pre-catalyst 1-Ru according to any one of claims 1 to 7 in the presence of a compound having a structure represented by a formula selected from 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13, 3-K1 in an amount ranging from 0.0001 mol % to 200 mol %.

15. 15. Use according to claim 13 or 14, wherein the reaction is carried out in an organic solvent selected from toluene, benzene, mesitylene, hexane, dichloromethane, dichloroethane, chlorobenzene, perfluorobenzene, perfluorotoluene, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, methyl tert-butyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2-ME-THF, 4-ME-THP, dioxane, DME, PAO, PEG, paraffin, ester of saturated fatty acid.

16. The use according to any one of claims 13 to 15, wherein the reaction is carried out in a solvent-free system.

17. The use according to any one of claims 13 to 16, wherein the reaction is carried out at a temperature of from 20 to 200°C.

18. The use according to any one of claims 13 to 17, wherein the reaction is carried out for a period of from 5 minutes to 48 hours.

19. The use according to any one of claims 13 to 18, wherein the 1-Ru compound is used in an amount of up to 10 mol %.

20. The use according to any one of claims 13 to 19, wherein the 1-Ru compound is used in an amount of 0.1 mol % or less.

21. Use according to any one of claims 13 to 20, wherein the 1-Ru compound is added to the reaction mixture in portions in solid form and / or continuously as a solution in an organic solvent by means of a pump.

22. 22. Use according to any one of claims 13 to 21, wherein the gaseous by-products of the reaction selected from ethylene, propylene, butylene are actively removed from the reaction mixture using an inert gas barbotage or vacuum.

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