E-selective metathesis catalysts

Abstract

The present invention relates to cationic molybdenum and tungsten complexes containing a heterocyclic nitrogen carbene (NHC) and preferably a halogen-containing aryloxy ligand. The catalysts are active in olefin metathesis reactions and provide for E-selectivity.

Description

E-SELECTIVE METATHESIS CATALYSTSFIELD OF THE INVENTION

[0001] The present invention relates to cationic molybdenum and tungsten complexes containing a N-heterocyclic carbene (NHC) and preferably a halogen-containing aryloxy ligand. The catalysts are active in olefin metathesis reactions and provide for E-selectivity.BACKGROUND OF THE INVENTION

[0002] It is known that most of the olefin metathesis catalysts such as Mo-, W- and Ru- based catalysts provide mixtures of cis / trans isomers when a new olefin with internal double bond is formed. Monoaryloxide pyrrolide (MAP)-type Mo- and W-based Schrock- alkylidenes containing bulky aryloxides were the first to catalyze the formation of cis (Z) C=C double bonds, while the first Ru-based Z-selective catalyst was introduced by Grubbs (Schrock and Grubbs, Nobel prize laureates 2005). Ru-dithiolate complexes also show high Z-selectivity, at relatively high catalyst loading, in the metathesis of terminal double bonds. In case of the cross metathesis of internal olefins it also proved to be stereo-retentive in the metathesis of internal olefins.

[0003] M.J. Benedikter et al., “Group 6 metal alkylidene and alkylidyne N-heterocyclic carbene complexes for olefin and alkyne metathesis”, Coordination Chemistry Reviews 415 (2020) 213315 disclose in Table 14 that some of the cationic NHC-containing molybdenum catalysts defined therein and bearing an aryloxy substituent display E- selectivity in the ring opening cross-metathesis (ROCM) of 2,3-disubstituted norbornenes using various substrates, whereas similar catalysts display Z-selectivity.

[0004] The authors of this publication propose in Figures 22 and 24 with respect to Table 14 that the steric bulk of the imido ligand in the metallacyclobutane formed by the catalyst and the substrate and / or chelating effects of the substrate with the catalyst may have an influence on the E / Z-ratio in the metathesis product.

[0005] WO 2015 / 162245 discloses N-heterocyclic carbene complexes of metal imido alkylidenes and metal oxo alkylidenes, and the use thereof as catalysts in olefinic metathesis reactions. The catalysts have the formulae I to IVas broadly defined therein, according to which A1stands for NR2or PR2, A2stands for CR2R2', NR2, PR2, 0 or S, A3stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2and R2' stand, inter alia, for a linear or branched Ci -Cw-alkyl group and, if A1and A2each stand for NR2or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X1or X2in formulas I to IV are the same or different and represent, inter alia, C1-C18 carboxylates and Ci-C -alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched Ci-Cw-alkylenoxy group, and R1and R1' in formulas I to IV are, inter alia, an aliphatic or aromatic group.

[0006] It is e.g. further known from I. Reim at al., “Toward E-selective Olefin Metathesis: Computational Design and Experimental Realization of Ruthenium Thio-lndolate Catalysts”, Topics in Catalysis, Volume 65, pages 448-461 (2022), that E-olefins, with substituents trans-disposed across the double bond, are important structural features in molecular entities ranging from antibiotics and anticancer therapeutics to precision polymers. This reference outlines that to date, metathetical access to E-olefin productscan be achieved only via “stereo-retentive” catalysts such as dithiocatechol Ru catalysts, which can transform stereochemically defined E-olefin substrates into E-configured products. The utility of stereo-retentive metathesis is limited by the cost and accessibility of the isomerically pure starting materials required.

[0007] Despite the advances in the art, the production of E-olefinic products represents an intellectually and economically attractive challenge.OBJECTS OF THE INVENTION

[0008] It is the object of the present invention to provide complexes by means of which the E-selective formation of olefins is achievable in an olefin metathesis reaction taking account of industrial requirements for the application of such catalysts. Industrially feasible, economical procedures require the application of highly active catalysts that allow the use of low catalyst loading, typically below 100 ppm or 0.01 mol%.SUMMARY OF THE INVENTION

[0009] This object is achieved with the compounds defined in independent claim 1. Contrary to the teaching of the prior art, the inventors have discovered that in particular halogen-containing aryloxy substituents in cationic molybdenum and tungsten complexes bearing a nitrogen-containing heterocyclic carbene are beneficially E-selective in an olefin metathesis reaction. In a preferred embodiment, the halogen-containing aryloxy substituent is a chlorine-containing aryloxy substituent.

[0010] The invention further relates to the molybdenum and tungsten complexes defined in independent claim 2.

[0011] Disclosed are also intermediates for the preparation of the inventive compounds according to claims 1 and 2. Beneficially, these compounds defined therein may also display catalytic activity in metathesis reactions, wherein the metathesis reaction is E- selective.

[0012] Claims depending on the independent claims represent preferred embodiments thereof.DETAILED DESCRIPTION OF THE INVENTION

[0013] In one aspect, the invention relates to a compound of formula I[M(NHC)(X)(Y)(Z)(L)n]AI whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is an aryloxy residue -OR4;L is a neutral ligand; n is 0 or 1 ;A is a non-coordinating anion; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H;R4is phenyl or phenyl substituted with at least one halogen atom;with the proviso that the compound of formula I is not a compound of one of the following formulae known from the prior art:, or

[0014] In one embodiment, the compound of formula I is not a compound of formula[M(NHC)(X)(Y)(-OC6F5)(L)n]A,wherein M, NHC, X, Y, L, n, and A have the meaning as defined above.

[0015] In another embodiment, in the compound of formula I, R4is phenyl or phenyl substituted with at least one halogen atom, wherein the halogen atom is selected from chlorine and bromine.

[0016] In a further aspect, the invention relates to a compound of formula II[M(NHC)(X)(Y)(Z)(L)n]AII whereinM is Mo or W; preferably Mo;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is an alkyloxy or aryloxy residue -OR4;L is a neutral ligand; n is 0 or 1 ;A is a non-coordinating anion; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H;R4is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;with the proviso that the following compounds known from the prior art are excluded:

[0017] In one embodiment, the compound of formula I is excluded from the compounds of formula II.

[0018] In still a further aspect, a compound of formula III[M(NHC)(X)(Y)(Z)(L)n]AmIII is disclosed, whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is triflate (trifluoromethanesulfonate, TfO’, CFsSOs’); or is halogenide selected from Cl- or Br; or is -OR4, wherein R4is C1-10 alkyl or Ce-uaryl, respectively optionally substituted;L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br;n is 0 or 1 ;A is a non-coordinating anion; m is 0, or 1 ; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H.

[0019] In a preferred embodiment, in the compound of formula III,(i) Z and L are TfO or Br, respectively, and n is 1 and m is 0; or(ii) Z is OR4and L is TfO or Br, and n is 1 and m is 0; or(iii) Z is TfO or Br, respectively, L is a neutral ligand, n is 0 or 1 and m is 1 .

[0020] In one embodiment, the compounds of formula III themselves possess activity in metathesis reactions, wherein the metathesis reaction is E-selective. This particularly applies to cationic compounds (iii), which are also according to the invention.

[0021] In another embodiment, the compounds of formula III are used as intermediates or starting material in the synthesis of the compounds of formula I and II.

[0022] In one embodiment, NHC in the compounds of formula I, II, and III, is selected from the group of following NHCs: a nitrogen-containing heterocyclic carbene containing the moiety of formula 6wherein R7and R8as defined in formula 6 are each independently H, unbranched or branched C1-20 alkyl, C5-9 cycloalkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen, and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbene carbon atom, the two nitrogen atoms and the optionally substituted alkenylene or alkylene group form a ring; or a nitrogen-containing heterocyclic carbene containing the moiety of formula 77 wherein Ar as defined in formula 7 is aryl, preferably phenyl, optionally substituted with one or more groups selected from: C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce- C14 aryl, C6-C14 aryloxy, or halogen; and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbon atom, the carbene carbon atom, the nitrogen atom and the optionally substituted alkenylene or alkylene group form a ring, which may optionally be bridged by an alkylene group.

[0023] In a preferred embodiment, NHC is selected from the group of following NHCs: wherein the carbene of formula 6 is a carbene of one of formulas 6a, 6b, 6c or 6d:6b6c or6d wherein R9and R10are each independently H, unbranched or branched C1-20 alkyl, or phenyl, wherein phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen; orR9and R10together with the carbon atoms to which they are attached are combined to form a carbocyclic 3 to 8 membered ring, preferably an aryl ring, more preferably C6H4;Y and Y' are halogen;further preferably, wherein NHC is of formula 6a or 6b, preferably wherein R9and R10as defined in formula 6a or 6b are H, respectively, and R7and R8as defined in formula 6a and 6b are mesityl, or 2,6-diisopropylphenyl; or wherein NHC is of formula(n = 1 -8).

[0024] In one embodiment, the carbene of formula 7 is a carbene of one of formulas 7a or 7b:7a wherein each R in formula 7a is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2- C12 alkenyl, Ce-C aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-C perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein two R which are separated by the C- CR2-C moiety can be combined with to form a cyclic system; or a carbene of formula 7bwherein each R in formula 7b is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2- C12 alkenyl, Ce-Cu aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein n is 1 , 2 or 3; preferably wherein R in formula 7b are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl.

[0025] In a preferred embodiment, the ligand of formula 7a is of formula 7a’7a’ wherein R12, R13, R14, and R15in formula 7a’ are each independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; and wherein R12and / or R13can be combined with R14and / or R15to form a cyclic system; or wherein the ligand of formula 7b is of formula 7b’:7b’ wherein R16, R17and R18in formula 7b’ are each independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, Ce-C aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, Ci-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom, preferably wherein R16, R17and R18in formula 7b’ are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl;

[0026] In a further preferred embodiment, NHC in formula 7 is a carbene of formula 7cwherein in formula 7c m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7c’or is a carbene of formula 7dwherein in formula 7d m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7d’7d’ or is a carbene of formula 7e7e or is a carbene of formula 7for is a carbene of formula 7g or 7hor is a carbene of formula 7i7i or is a carbene of formula 7kand wherein each R in one of formulas 7c to 7i is independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, Ci- 012 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; preferably wherein each R in formulas 7c to 7i is hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl.

[0027] In a preferred embodiment, NHC is selected from the group of following NHCs:(IMesH2 is also termed as SIMes)

[0028] In one embodiment, regarding the compounds of formulae I and III, the term “optionally substituted” with regard to any of R1, R2, and R3, means that substituents are independently selected from the group consisting of Ci-salkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxy may be in turn substituted with one or more of Ci-salkyl, Ci-salkoxy, halogen, nitro, N(Ci- salkyl)2, -NH-C(O)Ci-salkyl.

[0029] In one embodiment, regarding the compounds of formula II, the term “optionally substituted” with regard to any of R1, R2, R3, and R4means that substituents are independently selected from the group consisting of Ci-salkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxymay be in turn substituted with one or more of Ci-salkyl, Ci-salkoxy, halogen, nitro, N(Ci-5alkyl)2, -NH-C(O)Ci-5alkyl.

[0030] In one embodiment, one of R2and R3in the compounds according to formula I, II, and III, is hydrogen and the other one is -C(CH3)3 or -C(CH3)2CeH5. According to the invention, not both of R2and R3are H.

[0031] According to the invention, R4in the compound of formula I is selected from phenyl or phenyl substituted with at least one halogen atom.

[0032] In one embodiment, regarding the compound of formula I, R4is CeHs.

[0033] In another embodiment R4in the compound of formula I is phenyl substituted with at least one halogen atom.

[0034] In one embodiment, halogen is selected from F, Cl, and Br.

[0035] In one embodiment, phenyl contains as at least one halogen only F.

[0036] In a preferred embodiment, phenyl contains as at least one halogen only Cl.

[0037] In still another preferred embodiment, phenyl contains as at least one halogen only Br.

[0038] In one preferred embodiment, phenyl contains as at least one halogen F and Cl.

[0039] In another preferred embodiment, phenyl contains as at least one halogen F and Br.

[0040] In another preferred embodiment, phenyl contains as at least one halogen Cl and Br.

[0041] In another preferred embodiment, phenyl contains as at least one halogen F, Cl and Br.

[0042] In one embodiment, regarding the compound of formula I, R4is selected from a monofluorophenyl, a difluorophenyl, a trifluorophenyl, a tetrafluorophenyl, or from pentafluorophenyl.

[0043] In a preferred embodiment, phenyl contains as at least one halogen Cl. In one embodiment, R4is selected from monochlorophenyl, a dichlorophenyl, a trichlorophenyl, a tetrachlorophenyl, or from pentachlorophenyl.

[0044] In a preferred embodiment, R4is selected from 2-chlorophenyl; 2,3- dichlorophenyl, 2,4-dichlorphenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl; 3- chlorophenyl; 3,4-dichlorophenyl, 3,5-dichlorophenyl; 4-chlorophenyl; 2,3,4- trichlorophenyl, 2,3,5-trichlorophenyl, and 2,3,6-trichlorophenyl.

[0045] In another embodiment, R4is selected from monobromophenyl, a dibromophenyl, a tribromophenyl, a tetrabromophenyl, or from pentabromophenyl.

[0046] The term “neutral ligand” (L) as used in the compounds according to formula I, II, and III encompasses neutral molecule that donates an electron pair to the central metal of the complex.

[0047] In one embodiment, the neutral ligand L is selected from an ether, a phosphine, a nitrile, or a pyridine, dimethyl sulfoxide, acetone, and dimethylformamide.

[0048] In a preferred embodiment, the nitrile is selected from acetonitrile (ACN), t- butylnitrile (trimethylacetonitrile, pivalonitrile, PivCN), and benzonitrile.

[0049] The term “anionic ligand” as used herein with regard to the compounds of formula III, encompasses a negatively charged ion that donates an electron pair to the central metal of the complex. Anionic ligands in the meaning of the invention are triflate and halogenide such as chloride and bromide.

[0050] The term “coordinating anion” if used herein, encompasses a negatively charged ion that interacts strongly with a cation. E.g., in some embodiments, an anionic ligand may also be regarded as a coordinating anion.

[0051] The term “non-coordinating anion” (A) as used herein with regard to the compounds according to formula I, II, and III encompasses a negatively charged ion that interacts weakly with a cation.

[0052] In one embodiment, the non-coordinating anion is selected from the group consisting of perchlorate [CICM]’, tetrafluoro borate [BF4]", hexafluoro phosphate [PFe]’, hexafluoro antimonate [SbFe]’, tetraphenyl borate [BPh4]“, tetrakis(trifluoromethyl)borate [B(CF3)4]“, tetrakis(pentafluorophenyl)borate [B(C6Fs)4]_, tetrakis(3,5-bis- (trifluoromethyl)phenyl)borate [B{(3,5-di-CF3)C6H3}4]“, and tetrakis(nonoafluoro-t- butoxy)aluminate [AI{OC(CF3)3}4]“.

[0053] Accordingly, a formula such as [M(NHC)(X)(Y)(Z)(L)n]A, where A is a noncoordinating anion, has to be interpreted in the meaning of [M(NHC)(X)(Y)(Z)(L)n]+A_.

[0054] According to the invention, specific compounds known from the Benedikter reference or from WO 2015 / 162245 as referred to in the Background section, are excluded from the compounds according to formula I, respectively formula II.

[0055] In another aspect, the invention relates to the use of the compounds known from the Benedikter reference as referred to in the Background section and which have been disclaimed from the compound of formula I, i.e. , compounds of the following formulasfor an E-selective olefin metathesis reaction.

[0056] In another aspect, the invention relates to the use of the compounds known from the Benedikter reference as referred to in the Background section and which have been disclaimed from the compound of formula II, i.e., compounds of the following formulasfor an E-selective olefin metathesis reaction.

[0057] The compounds according to the invention can be used in all kinds of olefin metathesis reactions.

[0058] In one embodiment, the compounds according to the invention perform a crossmetathesis reaction (CM) including self- metathesis [(homo)-cross metathesis (HCM)].

[0059] In another embodiment, the compounds according to the invention perform a ringclosing metathesis reaction (RCM).

[0060] In another embodiment, the compounds according to the invention perform a ringopening metathesis reaction (ROM).

[0061] In another embodiment, the compounds according to the invention perform a ringopening metathesis polymerization (ROMP).

[0062] In another embodiment, the compounds according to the invention perform an acyclic diene metathesis reaction (ADMET).

[0063] Preferably, the olefins prepared in the metathesis reaction have predominantly E- configuration unless the formation thereof is sterically not possible, e.g., in the formation of small rings in RCM reactions.

[0064] The term “predominantly E-configuration” means that in the olefins formed at least 75 % are E-olefins while at the most 25 % are Z-olefins.

[0065] In another embodiment, at least 80 % are E-olefins while at the most 20 % are Z- olefins.

[0066] In another embodiment, at least 85 % are E-olefins while at the most 15 % are Z- olefins.

[0067] In another embodiment, at least 90 % are E-olefins while at the most 10 % are Z- olefins.

[0068] In another embodiment, at least 95 % are E-olefins while at the most 5 % are Z- olefins.

[0069] In another aspect, the invention relates to a method of performing a metathesis reaction, comprising: reacting a compound of formula I or II with one or more olefins.

[0070] In another aspect, the invention relates to a method of performing a metathesis reaction, comprising: reacting a compound of formula III[M(NHC)(X)(Y)(Z)(L)n]AmIII whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is triflate (TfO); or is halogenide selected from Cl- or Br-; or is -OR4, wherein R4is C1-10 alkyl or Ce-uaryl, respectively optionally substituted;L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br; n is 0 or 1 ;A is a non-coordinating anion; m is 0 or 1 ; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H; wherein in the compound of formula III(iii) Z is TfO or Br, respectively, n is 0 or 1 and m is 1 ; with one or more olefins.

[0071] In one embodiment, the metathesis reaction is the metathesis reaction of an unsaturated fatty acid ester with ethylene.EXAMPLES

[0072] The compounds according to the invention of formulae I, II or III were prepared according to known methods, e.g., methods disclosed in the Benedikter reference or in WO 2015 / 162245 as referred to in the Background section and as summarized below.

[0073] General Scheme for the synthesis of cationic molybdenum NHC aryloxy complexes according to formula I or formula II (DCM = dichloromethane):

[0074] General Scheme for the synthesis of cationic tungsten NHC aryloxy complexes according to formula I or formula II:

[0075] General Scheme for the synthesis of molybdenum NHC monoaryloxy monotriflate complexes according to formula II

[0076] Table 1 shows Schrock type carbenes. These catalysts were used for comparison.

[0077] Table 1Catalyst M Ri Li L2R2X002 Mo 2,6-iPr2Ph (CF3)2MeCO (CF3)2MeCO PhX052 Mo 2,6-iPr2Ph Me2Pyr BrPh4PhO PhX190 W 2,6-CI2Ph Me2Pyr BrPh4PhO PhX211 W 2,6-CI2Ph Me2Pyr BitetO 2-MeOPh(the term “bitetO” encompasses a ligand derived from 5,5',6,6',7,7',8,8'-octahydro-1 , 1 binaphthyl-2-ol which binds to M in its olate-form via proton abstraction from the phenolic OH group; Ph means phenyl)

[0078] Tables 2 and 3 show prepared Mo-NHC bistriflates, W-NHC dibromides, Mo- aryloxy tritiate, and cationic Mo-and W-triflates and bromides according to formula III (X359 to X963; Y is =CHCMe2C6H5):

[0079] Table 2:Catalyst M Ri NHCZX359 Mo 2,6-Me2Ph IMes TfO TfOX793 Mo 2,6-Me2Ph SIMes TfO TfOX457 Mo 2,6-CI2Ph IMes TfO TfOX883 Mo 3,5-Me2Ph IMes TfO TfOX932 W 2,6-CI2Ph IMes Br BrX933 W 2,6-CI2Ph SIMes Br BrX959 W 3,5-Me2Ph IMes Br BrX942 Mo 2,6-Me2Ph IMes TfO PhOX943 Mo 2,6-Me2Ph IMes TfO 2-CIPhOX944 Mo 2,6-Me2Ph IMes TfO CeFsOX1043 Mo 2,6-Me2Ph IMes TfO 2,6-CI2Ph(SIMes means: 1 ,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene;IMes means: 1 ,3-bis(2,4,6-trimethylphenyl)-imidazole-2-ylidine)

[0080] Table 3Catalyst M Ri NHC Z L A'X930 Mo 2,6-Me2Ph IMes TfO - BArFX931 Mo 2,6-Me2Ph SIMes TfO - BArFX964 Mo 2,6-Me2Ph IMes TfO - BPh4X969 Mo 3,5-Me2Ph IMes TfO - BArFX955 Mo 2,6-CI2Ph IMes TfO - BArFX937 W 2,6-CI2Ph IMes Br PivCN BArFX963 W 3,5-Me2Ph IMes Br PivCN BArF(BArF as used herein means tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate [B{(3,5-di- CF3)C6H3}4]-)

[0081] Table 4 shows prepared cationic Mo- and W-NHCs according to formula I (X945 to X968; X979 to X954) and according to formula II (X973).

[0082] Table 4Catalyst M Ri NHC Z L A'X945 Mo 2,6-Me2Ph IMes PhO - BArFX946 Mo 2,6-Me2Ph IMes 2-CIPhO - BArFX947 Mo 2,6-Me2Ph IMes CeFsO - BArFX948 Mo 2,6-Me2Ph IMes 2,6-CI2PhO - BArFX949 Mo 2,6-Me2Ph IMes 2,5-CI2PhO - BArFX950 Mo 2,6-Me2Ph IMes 3,5-CI2PhO - BArFX956 Mo 2,6-Me2Ph SIMes 2,6-CI2PhO - BArFX957 Mo 2,6-CI2Ph IMes 2,6-CI2PhO - BArFX970 Mo 3,5-Me2Ph IMes 2,6-CI2PhO ACN BArFX971 Mo 2,6-Me2Ph IMes 2,6-CI2PhO - BPh4X1041 Mo 2,6-Me2Ph IMes 2,6-CI2PhO ACN PF6X1042 Mo 2,6-Me2Ph IMes PhO - BF4X972 Mo 2,6-Me2Ph IMes 2,6-Br2PhO - BArFX712 Mo Ad IMes CeFsO ACN BArFX966 W 2,6-CI2Ph IMes 2,6-CI2PhO PivCN BArFX967 W 2,6-CI2Ph IMes CeFsO PivCN BArFX968 W 2,6-CI2Ph IMes PhO PivCN BArFX973 W 2,6-CI2Ph IMes HMTO PivCN BArFX979 W 2,6-CI2Ph IMes 2,6-Br2PhO PivCN BArFX965 W 3,5-Me2Ph IMes 2,6-CI2PhO PivCN BArFX977 W 3,5-Me2Ph IMes CeFsO PivCN BArFX980 W 3,5-Me2Ph IMes 2,6-Br2PhO PivCN BArFX954 W 3,5-Me2Ph IMes PhO PivCN BArF(HMTO = hexamethyl terphenolate = 2,5-dimesitylphenolate; ACN=acetonitrile, PivCN=pivaloylnitrile; Ad = 1-adamantyl)

[0083] The catalytic activity and stereo-selectivity of the prepared molybdenum and tungsten NHC complexes were tested in cross-metathesis and ethenolysis reactions and compared to selected MAP catalysts.

[0084] Specific examples

[0085] All reactions were performed in nitrogen-filled glovebox, using oven-dried glassware. Toluene and pentane were distilled over sodium / benzophenone. Dichloromethane was distilled over CaH2. All solvents were further dried by storage over molecular sieves (4A).

[0086] Synthesis of X359Mes OTfX359

[0087] Bistriflate (Mo(2,6-Me2PhN)(CHCMe2Ph)(TfO)2xDME) (39.56 g) was dissolved in toluene (700 mL). The clear, brownish orange solution was cooled to -20°C. IMes (16.373 g) was dissolved in toluene (150 mL) to give clear, colorless solution. The cold solution of IMes in toluene was added slowly. The reaction mixture became dark. Yellow solid precipitated after 10 minutes. The reaction mixture was stirred at -20°C for one hour, then slowly allowed to warm up to 25°C and stirred for additional 3 hours. The precipitated yellow solid was filtered, washed with cold toluene (3x30 mL) and pentane (3x30 ml) then dried under nitrogen stream. Yield was 45 g (88%)1H NMR (300MHz, CD2CI2, 296K) 5 = 13.18 (s, Mo=CH-, 1 H), 7.23-7.03 (m, Ar-H, 8H), 7,96 (broad, Mes-H, 2H), 7.96 (broad, Mes-H, 2H), 6.56 (broad s, Imidazole CH, 2H), 2.60 (broad, Mes-Me, 3H), 2.25 (s, Ar-H, 3H), 2.13 (s, Ar-H, 3H), 1.98 (s, CHCMe2Ph, 3H), 1.96 (s, Ar-H, 3H), 1.88 (broad, Mes-Me, 3H), 1.30 (s, CHCMe2Ph, 3H) ppm.19F NMR (282MHz, CD2CI2) 5 = -74.94 (broad s, OTf, 3F), -76.52 (broad s, OTf, 3F) ppm.

[0088] Synthesis of X930X930

[0089] To the solution of X359 (6.65 g) in DCM (35 mL), sodium tetrakis(3,5-bis- (trifluoromethyl)phenyl)borate (6.20 g) was added portion-wise. The reaction mixture was stirred at 25°C overnight. The obtained orange-yellow suspension was filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and the resulting light brown foam was triturated in pentane. Filtration was followed by drying yielding 11 g (94%) of yellow powder.1H NMR (300MHz, CD2CI2, 296K) 5 = 13.05 (s, Mo=CH-, 1 H), 7.72 (m, B-Ar-H(orf / 7O), 8H), 7.56 (s, B-Ar-H(para), 4H), 7.46 (s, Imidazole CH, 2H), 7.14-7.00 (m, Ar-H, 5H), 6.97 (t, -CMe2Ph(meta), 2H), 6.92 (broad d, Ar-H, 2H), 6.85 (broad s, Ar-H, 2H), 6.76 (t, Ar-H, 1 H), 2.33 (s, Me, 6H), 2.08 (s, Me, 6H), 2.06 (broad, Me, 3H), 1.90 (broad s, Me, 6H), 1.84 (broad, Me, 3H), 1.14 (s, CHCMe2Ph, 3H), 1.00 (s, CHCMe2Ph, 3H) ppm.19F NMR (282MHz, CD2CI2) 5 = -62.88 (s, Ar-CF3, 24F), -73.58 (s, OTf, 2F) ppm.

[0090] Synthesis of X942

[0091] To the cold solution of X359 (8.55 g) in DCM (50 mL), lithium phenolate was added portion-wise as a solid at -35°C. The reaction mixture was allowed to warm up and stirred at 25°C for 3 hours. The orange-yellow suspension was filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and the resulting light brown foam was triturated in pentane. Filtration was followed by drying yielding 7.3 g (91 %) of yellow powder.1H NMR (300MHz, C6D6, 323K) 5 = Two isomers (a and b), 14.88a (s, Mo=CH-, 1 H), 13.92b (s, Mo=CH-, 1 H), 7.45a+b (m, Ar-H, 2H), 7.27a (dd, Ar-H, 1 H), 7.21b (m, Ar-H, 1 H), 7.19a (m, Ar-H, 2H), 7.09-7.02a+b (m, Ar-H, 2H), 6.93-6.73 (m, Ar-H, 3H), 6.65a+b (m, Ar- H, 1 H), 6.53a+b (m, Ar-H, 1 H), 6.44a+b (m, Ar-H, 1 H), 6.41a+b (m, Ar-H, 2H), 6.30a (m, Ar- H, 1 H), 6.04b (s, Imidazole CH, 2H), 5.95a (s, Imidazole CH, 2H), 2.74b (broad s, Me, 3H), 2.46a (broad s, Me, 3H), 2.25a (broad s, Me, 3H), 2.19b (broad s, Me, 3H), 1.99b (s, Me, 6H), 1.95a (s, Me, 3H), 1.91a (s, Me, 3H), 1.80b (s, Me, 3H), 1.71a (s, Me, 3H), 1.69b (s, Me, 3H), 1.56a (s, Me, 3H) ppm.19F NMR (282MHz, C6D6, 323K) 5 = -77.49b (broad s, OTf, 3F), -77.58a (broad s, OTf, 3F) ppm.

[0092] Synthesis of X948X948

[0093] To the cold solution of X930 (11.00 g) in 50 mL of DCM, lithium 2,6- dichlorophenolate (1.11 g) was added portion-wise as a solid at -35°C. The reaction mixture was allowed to warm up and stirred at 25°C for 3 hours. The orange-yellowsuspension was filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and the resulting light brown foam was triturated in pentane. Filtration was followed by drying yielding 10.46 g (94%) of yellow powder.1H NMR (300MHz, CD2Cl2, 296K) 6 = 12.92 (s, Mo=CH-, 1 H), 7.73 (m, B-Ar-H(ort / ?o), 8H), 7.56 (s, B-Ar-H(para), 4H), 7.30 (d, Ar-H, 2H), 7.21-7.10 (m, Ar-H, 4H), 6.99-6.90 (m, Ar- H, 6H), 6.84 (t, Ar-H, 1 H), 6.61 (s, Imidazole CH, 2H), 2.15 (broad s, Me, 6H), 2.13 (broad s, Me, 3H), 2.12 (broad s, Me, 3H), 2.10 (broad, Me, 3H), 1.88 (s, CHCMe2Ph, 3H), 1.35 (s, CHCMe2Ph, 3H) ppm.19F NMR (282MHz, CD2CI2, 296K) 5 = -62.87 (s, B-Ar-CF3) ppm.

[0094] Synthesis of W(3,5-Me2RhN)(CHCMe2Ph)(Br)2xDME

[0095] The corresponding bistriflate (12.00 g) and KBr (10.4 g, 6 eq.) were mixed in DCM / DME (110 mL / 12 mL) and the reaction mixture was stirred at 25°C for 4 days. The reaction mixture was filtered, and the solvent was evaporated leaving brick red solid, which was suspended in pentane, filtered and dried. 9.12 g (91 %) of red powder was obtained.1H NMR (300MHz, CD2CI2, 296K) 5 = 10.58 (s, W=CH-, 1 H), 7.78 (d, Ph-H(ort / ?o), 2H), 7.43 (s, N-Ar-H(ort / ?o), 2H), 7.30 (t, Ph-H(meta), 2H), 7.06 (t, Ph-H(para), 1 H), 6.54 (s, N- Ar-H(para), 1 H), 3.24 (s, -OMe, 6H), 3.14 (broad s, -O-CH2-CH2-O-, 4H), 1.94 (broad s, Me, 6H), 1.92 (broad s, Me, 6H) ppm.

[0096] Synthesis of X959X959

[0097] (W(3,5-Me2PhN)(CHCMe2Ph)(Br)2xDME (9.1 g) was dissolved in toluene (350 mL). The clear, brownish orange solution was cooled to -20°C. IMes (4.04 g) was dissolved in toluene (50 mL) to give clear, colorless solution. The cold solution of IMes in toluene was added slowly. The reaction mixture was stirred at -20°C for one hour, then slowly allowed to warm up to 20°C and stirred at 25°C overnight. The reaction mixture was concentrated by evaporation of half of the solvent. The precipitated yellow solid was filtered, washed with cold toluene and pentane then dried under nitrogen stream. 8.92 g (74%).1H NMR (300MHz, CD2CI2, 296K) 5 = 9.64 (s, W=CH-, 1 H), 7.21 (m, Ar-H, 5H), 7.09 (s, Ar-H, 2H), 6.79 (broad s, Ar-H, 1 H), 6.54 (overlapping broad signals, 6H), 2.25 (s, N- ArMe2, 6H), 2.13- 2.03 (broad signals, Mes-Me, 18H), 1.64 (s, CHCMe2Ph, 3H), 1.47 (s, CHCMe2Ph, 3H) ppm.

[0098] Synthesis of X963

[0099] To a suspension of sodium tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate (8.76 g) in DCM (16 mL), trimethylacetonitrile (PivCN, 1.1 mL) was added (dried over molecular sieve) followed by the addition of a solution of X959 (8.90 g) in 50 mL DCM. The reaction mixture was stirred overnight at 25°C, then filtered through a pad of Celite. The mother liquor was evaporated to dryness and the obtained brownish foam was triturated in pentane. Filtration was followed by drying yielding 16.4 g (94%) of yellow powder.1H NMR (300MHz, CD2CI2, 296K) 5 = 10.35 (s, W=CH-, 1 H), 7.72 (m, B-Ar-H(ort / ?o), 7.56 (s, B-Ar-H(para), 7.32-7.24 (m, -Ph (meta and para), 3H), 7.22 (s, N-Ar-H(ort / ?o), 2H), 7.15 (m, -Ph (ortho), 2H), 6.87 (broad s, N-Ar-H(para), 1 H), 6.62 (boad s, Mes-Ar- H(meta), 4H), 6.36 (broad s, Imidazole CH, 2H), 2.25 (s, Mes-Me, 6H), 2.12 (s, Mes-Me, 12H), 1.96 (s, Mes-Me, 6H), 1.63 (s, CHCMe2Ph, 3H), 1.58 (s, CHCMe2Ph, 3H), 1.15 (s, N C-tBu, 9H) ppm.19F NMR (282MHz, CD2CI2, 296K) 5 = -62.9 ppm.

[0100] Synthesis of X965

[0101] To the cold solution of X963 (6.00 g) in 50 mL of DCM, lithium 2,6- dichlorophenolate (574 mg) was added portion-wise as a solid at -35°C. The reaction mixture was allowed to warm up and stirred at 25°C for 3 hours. The orange-yellow suspension was filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and the resulting light brown foam was triturated in pentane. Filtration was followed by drying yielding 5.85 g (93%) of yellow powder.1H NMR (300MHz, CD2CI2, 296K) 5 = 11 .96 (s, W=CH-, 1 H), 7.72 (m, B-Ar-H(ort / ?o), 7.56 (s, B-Ar-H(para), 7.34-7.14 (m, Ar-H, 7H), 7.21 (s, Ar-H, 2H), 6.79 (t, OPhCI2-H(para), 1 H), 6.75 (broad s, Ar-H, 3H), 6.63 (broad s, Ar-H, 2H), 6.36 (broad s, Imidazole CH, 2H), 2.22 (s, Me, 6H), 2.16 (s, Me, 6H), 1.99 (s, Me, 6H), 1.87 (s, Me, 6H), 1.74 (s, Me, 3H), 1.69 (s, Me, 3H), 0.73 (s, N=C-fBu, 9H) ppm.19F NMR (282MHz, CD2CI2, 296K) 6 = -62.9 ppm.

[0102] Synthesis of Mo(Me2PhN)(CHCMe2Ph)(IMes)(2,6Cl2PhO)(OTf) X1043To the cold solution of X359 (1.5 g) in DCM (15 mL) Lithium 2,6-dichlorophenolate (267 mg) was added portion-wise as a solid at -10°C. The reaction mixture was allowed to warm up and stirred at 25°C for 3 hours. The orange-yellow suspension was filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and suspended in minimum amount of DCM, stirred then filtered and washed with pentane. Filtration was followed by drying yielding 1.12 g (73%) of yellow powder.1H NMR (400MHz, CD2Cl2, 298K) 6 = 14.25 ppm

[0103] Synthesis of X1041To the solution of Mo(2,6-Me2PhN)(CHCMe2Ph)(IMes)(2,6-Cl2PhO)(OTf) (500 mg) in 6 mL of DCM sodium hexafluorophosphate was added portion-wise as a solution in acetonitrile at 25°C. The reaction mixture was stirred at 25°C for 3 hours. The orangeyellow suspension was evaporated to dryness. The solid was decantated in toluene, and toluene was evaporated three times. The residue was dissolved in DCM and filtered through Celite, the filter pad was washed with DCM. The mother liquor was evaporated to dryness and the resulting yellow solid was triturated in pentane. Filtration was followed by drying yielding 327 mg (63%) of yellow powder.1H NMR (400MHz, CD2Cl2, 298K) 5 = 14.05 (s, alkylidene, 1 H), 7.26-7.21 (m, ArH, 3H), 7.24 (s, mesityl ArH, 4H), 7.13 (m, ArH, 2H), 7.06 (m, ArH, 1 H), 6.99 (m, ArH, 2H), 6.73 (t, ArH, 1 H), 6.72 (s, IMes =CH, 2H), 6.70 (d, ArH, 2H), 2.36 (s, imido Me, 6H), 2.19 (s, mesityl Me, 6H), 2.01 (s, mesityl Me, 6H), 2.00 (s, mesityl Me, 6H), 1.84 (s, neophylidene, 3H), 1.69 (broad s, neophylidene Me, 3H), 1 ,56 (s, MeCN Me, 3H)19F NMR (376MHz, CD2CI2, 298K) 5 = -73.4 (d, 1 JP-F= 708.6Hz, 6F).

[0104] Metathesis of terminal olefins

[0105] Based on the test reactions using terminal olefins, molybdenum NHC bistriflates, tungsten NHC dibromides and molybdenum NHC monotriflate-monoaryloxy complexes showed less activity at 100 ppm catalyst loading compared to cationic molybdenum and tungsten NHC complexes.

[0106] Cationic molybdenum and tungsten NHC complexes showed significantly higher activity, among those cationic molybdenum NHC aryloxy complexes showed very high catalytic activity even below 100 ppm. Moreover, the cationic molybdenum aryloxy derivatives showed high E-selectivity.

[0107] Cross Metathesis of 1 -decene and methyl 9-decenoate

[0108] Yield (%) = 100 x n(P) / n(9DAME). In case of 1 to 1 ratio of starting materials, the maximum achievable yield in closed system was 50%.

[0109] Table 5 shows the results of the cross-metathesis of 1 -decene and methyl 9- decenoate using cationic Mo- and W-NHCs:

[0110] Table 5CatalystLoadin9 yield (%) E / Z y (PPm)v’X930 101 3,4 79 / 21X931 100 6,2 85 / 15X969 100 4,1 87 / 13X955 101 4,6 89 / 11X937 101 19,0 70 / 30X963 100 1 ,1 26 / 74X964 100 0,7 91 / 9X946 100 47,2 96 / 4X945 101 45,4 91 / 9X947 101 41 ,0 90 / 10X948 100 48,9 98 / 2X949 100 40,5 88 / 12X950 100 44,4 93 / 7X956 100 43,4 98 / 2X957 100 42,4 98 / 2X965 100 35,0 75 / 25X966 101 30,0 82 / 18X971 100 36,2 99 / 1X712 100 11 ,1 61 / 39

[0111] Table 6 shows the cross-metathesis of 1 -decene and methyl 9-decenoate using selected cationic Mo- and W-NHCs (X948 to X954) at 75 ppm, and comparison with MAP catalysts (X002 to X211) from Table 1 :

[0112] Table 6„ . , . Loading YieldCatalVst(ppm) (%)E / ZX948 75 31 ,6 98 / 2X956 75 19,5 98 / 2X957 75 24,2 97 / 3X970 75 34,9 78 / 22X971 75 12,2 98 / 2X972 75 30,1 98 / 2X965 75 15,1 71 / 29X966 75 7,5 81 / 19X967 75 0,4 75 / 25X968 75 7,5 75 / 25X973 75 19,5 82 / 18X977 75 0,0 - / -X979 75 10,7 87 / 13X980 75 15,2 71 / 29X954 75 0,7 51 / 49Reference reactionsX002 75 2,3 66 / 34X052 75 1 ,0 81 / 19X190 75 2,3 71 / 29X190 100 22,7 72 / 28X211 75 0,2 - / -X211 100 43,7 3 97

[0113] Self-metathesis of 1 -decene

[0114] Table 7 shows the results of the self-metathesis of 1-decene using compounds according to the invention and comparative complexes from Table 1 :

[0115] Table 7„ , Loading YieldCata vst , ° ,n / xE / Z y (ppm) (%)X948 31 48,7 94 / 6X956 34 47,5 - / -X957 33 48,7 92 / 8X970 33 48,5 92 / 8X971 34 10,7 - / -X972 33 48,4 95 / 5X965 33 47,4 88 / 12X966 34 41,7 90 / 10X967 31 9,3 73 / 27X968 34 44,5 89 / 11X973 34 45,8 91 / 9X979 34 46,8 92 / 8Reference reactionsX002 33 39,8 86 / 14X052 31 27,3 90 / 10X190 34 29,4 83 / 17X211 34 29,3 3 / 97

[0116] Self-metathesis of methyl 9-decenoate

[0117] Table 8 shows the results of the self-metathesis of methyl 9-decenoate using compounds according to the invention and comparative complexes from Table 1 :

[0118] Table 8Catalyst Loading (ppm) Yield (%) E / ZX948 75 36,5 98 / 2X956 75 23,0 98 / 2X957 75 22,8 97 / 3X970 75 36,5 79 / 21X971 76 26,6 98 / 2X972 75 30,5 98 / 2X965 75 5,5 72 / 28X966 75 4,7 81 / 19X967 75 0,5 72 / 28X968 74 2,8 74 / 26X973 75 18,6 83 / 17X979 75 3,9 87 / 13Reference reactionsX002 74 0,8 - / -X052 75 0,3 - / -X190 76 0,5 - / -X211 75 0,2 / -

[0119] Self-metathesis of methyl 9-decenoate, scale-up

[0120] In a 2L round-bottomed flask, 265 mg of X948 (75 ppm) was added to 389 g of methyl 9-decenoate. The reaction mixture was stirred at 25°C under dynamic vacuum of 50 mbarfor 3 hours. 1 mL of methanol was added to the reaction mixture and the product was isolated by vacuum distillation. 300 g of dimethyl (E)-9-octadecendioate (Yield= 42%, out from the maximum of 50%). E / Z ratio: 97 / 3, was determined by GC.

[0121] Cross Metathesis of (Z)-1 ,3-hexadiene and methyl 9-decenoate

[0122] Cross-metathesis of the conjugated diene, (Z)-1 ,3-hexadiene, with methyl 9- decenoate using the Z-selective X211 provides methyl (Z,Z)-9,11 -tetradecadienoate, the E-selective X948 and X971 gave another stereo-isomer methyl (E,Z)-9,11- tetradecadienoate.

[0123] Table 9 shows the results of the cross-metathesis of (Z)-1 ,3-hexadiene and methyl 9-decenoate using the complexes according to the invention and comparative complexes from Table 1 :

[0124] Table 9„ . , , Yield Sei. (%)Catalyst Loading (ppm) (9EnZ)X948 200 32,4 99X956 200 19,0 99X957 200 4,4 99X965 200 8,4 75X966 200 12,5 87X971 199 32,4 99Reference reactionsX052 200 12,5 93X190 200 7,6 72X211 200U'898*Sel. (%): 100

[0125] Cross Metathesis of allyl acetate (AAc) and methyl 9-decenoateMaximum Yield = 66%, as n(AAc) / n(9DAME)= 2

[0126] Table 10 shows the results of the cross-metathesis of allyl acetate (AAc) and methyl 9-decenoate using complexes according to the invention and comparative complexes from Table 1 .

[0127] While cross metathesis of allyl acetate with methyl 9-decenoate did not occur in case of MAP type catalysts, the cationic Molybdenum NHC aryloxy complex, X948 proved to be an excellent catalyst for this transformation.

[0128] Table 10YieldCatalyst Loading (ppm) E / Z(%)X948 200 57,3 98 / 2X965 200 0,2 72 / 28X966 200 4,5 79 / 21X973 200 6,6 79 / 21Reference reactionsX002 199 0 - / -X052 200 0,6 - / -X190 200 0,0 - / -X211 200 0,0 /

[0129] Cross metathesis of allyl acetate with methyl 9-decenoate, synthesis of methyl (E)-11-acetoxy-undecenoate, Scale-up experiment

[0130] 375 g of allyl acetate and 345 g of methyl 9-decenoate were mixed in a 2L round- bottomed flask equipped with a reflux condenser. 0.85 mL methylaluminoxane (MMAO) (7wt% in toluene, 350 ppm) was added and the mixture was stirred at 25°C for 4 hours. After the pre-treatment period, 460 mg of X948 (50 ppm) was added and the reaction mixture was stirred under dynamic vacuum (500 mbar) at 25°C for 4 hours and for additional 20 hours at atmospheric pressure. 1 mL of methanol was added to the reaction mixture and the product was isolated by vacuum distillation. 281 g of methyl (E)-11 - acetoxy-undecenoate (Yield= 58%). E / Z ratio: 97.8 / 2.2, was determined by GC.1H NMR (300MHz, CDCh, 296K) 5 = 5.76 (ttd,3JCH->CH = 15.3Hz,3JCH-CH2 = 6,7Hz,4JCH->CH2 =1 .0HZ, -O-CH2-CH=CH-, 1 H), 5.55 (ttd,3JCH->CH = 15.3Hz,3JCH-CH2 = 6,4Hz,4JCH->CH2-O =1 .3HZ, -O-CH2-CH=CH-, 1 H), 4.50 (qd,3JO-CH2->CH = 6,4Hz,4JO-CH2->CH = 1.3Hz,5JO-CH2->CH2 < 1 Hz, -O-CH2-CH=CH-, 1 H), 3.66 (s, Me-OC(O)-, 3H), 2.30 (t,3JCH2- >CH2 = 7.7Hz, Me-OC(O)-CH2-, 2H), 2.06 (s, Me-C(O)-O, 3H), 2.04 (broad q, =CH-CH2- CH2-, 2H), 1 .61 (broad quintet, Me-OC(O)-CH2-CH2-, 2H), 1 .35-1 .29 (m, -CH2-, 8H) ppm.

[0131] Metathesis of internal olefins

[0132] Cross Metathesis of (E)-9-octadecene with methyl 9-decenoate

[0133] Table 11 shows the results of the cross-metathesis of (E)-9-octadecene with methyl 9-decenoate. Molybdenum and tungsten metathesis catalysts are, in general, less reactive toward internal olefins. Yet, the cationic Mo / W NHC complexes showed higher activity than the tested MAP catalysts from Table 1. Cationic NHC complexes also showed ability to cleave C=C double bond of trans-olefins.

[0134] Table 11YieldCatalyst Loading (ppm) E / Z(%)X946 151 13,7 96 / 4X945 150 13,4 91 / 9X947 150 9,1 90 / 10X948 150 20,6 98 / 2X949 151 7,8 87 / 13X950 150 12,8 93 / 7X956 150 9,9 99 / 1X957 150 9,9 98 / 2X970 151 46,0 89 / 11X971 149 10,3 99 / 1X972 149 17,2 99 / 1X965 158 47,1 86 / 14X966 150 23,7 84 / 16X967 150 1,8 73 / 27X968 150 13,3 78 / 22X973 150 31,0 84 / 16X979 150 25,4 89 / 11X977 150 3,2 91 / 9X980 150 40,1 85 / 15X954 149 36,9 80 / 20Reference reactionsX002 151 18,6 72 / 28X052 150 7,8 84 / 16X190 150 15,9 82 / 18X211 150 2,9 4 / 96

[0135] Cross Metathesis of (Z)-9-octadecene with methyl 9-decenoate

[0136] Table 12 shows the results of the cross-metathesis of (Z)-9-octadecene with methyl 9-decenoate:

[0137] Table 12YieldCatalyst Loading (ppm) E / Z(%)X946 100 1,4 96 / 4X945 99 1,8 92 / 8X947 99 2,1 91 / 9X948 99 2,0 98 / 2X949 100 1,5 89 / 11X950 100 2,4 93 / 7X956 101 0,5 97 / 3X957 100 0,6 95 / 5X970 99 17,4 82 / 18X971 100 0,5 99 / 1X972 100 1,4 98 / 2X965 100 22,6 77 / 23X966 101 12,7 84 / 16X967 100 0,4 90 / 10X968 100 7,1 79 / 21X973 99 17,4 84 / 16X977 100 1,5 20 / 80X979 101 7,1 89 / 11X980 100 17,1 77 / 23X954 99 2,6 22 / 78Reference reactionsX002 99 5,5 73 / 27X052 101 0,1 81 / 27X190 99 2,4 74 / 19X211 100 3,4 2 / 26

[0138] Ethenolysis of methyl elaidate (methyl (E)-9-octadecenoate)

[0139] Contrary to other Mo / W complexes, ethenolysis of trans-double bond is also feasible by using cationic NHC catalysts.

[0140] Table 13 shows the results of ethenolysis of methyl elaidate (methyl (E)-9- octadecenoate) at ab exemplary temperature of 50 °C:

[0141] Table 13Catalyst Loading (ppm) YfDAME, %)X945 500 29,5X946 500 33,8X947 500 37,0X948 500 47,3X949 500 19,9X950 500 35,8X954 500 4,6X956 500 12,3X957 500 41,5X965 500 42,8X966 500 24,6X967 500 4,4X968 500 14,2X970 500 50,4X971 500 2,3X973 500 37,1X977 500 1,8X979 500 19,2

Claims

CLAIMS1 . Compound of formula I[M(NHC)(X)(Y)(Z)(L)n]AI whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is an aryloxy residue -OR4;L is a neutral ligand; n is 0 or 1 ;A is a non-coordinating anion; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H;R4is phenyl or phenyl substituted with at least one halogen atom;with the proviso that the compound of formula I is not a compound of one of the following formulae:, orCompound of formula II[M(NHC)(X)(Y)(Z)(L)n]AII whereinM is Mo or W; preferably Mo;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is an alkyloxy or aryloxy residue -OR4;L is a neutral ligand; n is 0 or 1 ;A is a non-coordinating anion; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H;R4is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; with the proviso that the compound of formula II is not a compound of one of the following formulae:preferably wherein also the compounds of formula I as defined in claim 1 are excluded.

3. Compound of any one of claim 1 or 2, wherein NHC is selected from the group of following NHCs: a nitrogen-containing heterocyclic carbene containing the moiety of formula 6wherein R7and R8as defined in formula 6 are each independently H, unbranched or branched C1-20 alkyl, C5-9 cycloalkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen, and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbene carbon atom, the two nitrogen atoms and the optionally substituted alkenylene or alkylene group form a ring; or a nitrogen-containing heterocyclic carbene containing the moiety of formula 77 wherein Ar as defined in formula 7 is aryl, preferably phenyl, optionally substituted with one or more groups selected from: C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryl, C6-C14 aryloxy, or halogen; and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbon atom, the carbene carbon atom, the nitrogen atom and the optionally substituted alkenylene or alkylene group form a ring, which may optionally be bridged by an alkylene group; preferably wherein the carbene of formula 6 is a carbene of one of formulas 6a, 6b, 6c or 6d:6b6c or6d wherein R9and R10are each independently H, unbranched or branched C1-20 alkyl, or phenyl, wherein phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen; orR9and R10together with the carbon atoms to which they are attached are combined to form a carbocyclic 3 to 8 membered ring, preferably an aryl ring, more preferably C6H4;Y and Y' are halogen; further preferably, wherein NHC is of formula 6a or 6b, preferably wherein R9and R10as defined in formula 6a or 6b are H, respectively, and R7and R8as defined in formula 6a and 6b are mesityl, or 2,6-diisopropylphenyl; or wherein NHC is of formula(n = 1-8).

4. Compound of any one of claims 1 to 3, wherein NHC is selected from:Compound of claim 3, wherein the carbene of formula 7 is a carbene of one of formulas 7a or 7b:wherein each R in formula 7a is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, Ce-Cu aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein two R which are separated by the C-CR2-C moiety can be combined with to form a cyclic system; or a carbene of formula 7b7b wherein each R in formula 7b is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, Ce-Cu aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein n is 1 , 2 or 3; preferably wherein R in formula 7b are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl; preferably wherein the ligand of formula 7a is of formula 7a’wherein R12, R13, R14, and R15in formula 7a’ are each independently hydrogen, C1- C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; and wherein R12and / or R13can be combined with R14and / or R15to form a cyclic system; or wherein the ligand of formula 7b is of formula 7b’:wherein R16, R17and R18in formula 7b’ are each independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom, preferably wherein R16, R17and R18in formula 7b’ are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl; further preferably wherein NHC in formula 7 is a carbene of formula 7cwherein in formula 7c m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7c’7c’ or is a carbene of formula 7dwherein in formula 7d m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7d’7d’ or is a carbene of formula 7eor is a carbene of formula 7for is a carbene of formula 7g or 7hor is a carbene of formula 7kand wherein each R in one of formulas 7c to 7i is independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; preferably wherein each R in formulas 7c to 7i is hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl.

6. Compound of any one of claims 1 and 3 to 5 as far as depending on claim 1 , wherein the term “optionally substituted” with regard to any of R1, R2, and R3, means that substituents are independently selected from the group consisting of Ci-salkyl, Cisalkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxy may be in turn substituted with one or more of Cisalkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl; or compound of any one of claims 2 and 3 to 5 as far as depending on claim 2, wherein the term “optionally substituted” with regard to any of R1, R2, R3, and R4means that substituents are independently selected from the group consisting of Ci-salkyl, Cisalkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxy may be in turn substituted with one or more of Ci- salkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl.

7. Compound of any one of claims 1 to 6, wherein one of R2and R3is hydrogen and the other one is -C(CH3)3 or -C(CH3)2C6Hs.

8. Compound of any one of claims 1 and 3 to 7 as far as depending on claim 1 , wherein R4is selected from phenyl; or from phenyl containing as at least one halogen only F; or from phenyl containing as at least one halogen only Cl; or from phenyl containing as at least one halogen only Br; or from phenyl containing as at least one halogen F and Cl; or from phenyl containing as at least one halogen F and Br; or from phenyl containing as at least one halogen Cl and Br; or from phenyl containing as at least one halogen F, Cl and Br.

9. Compound of any one of claims 1 to 8, wherein the neutral ligand L is selected from an ether, a phosphine, a nitrile, or a pyridine, dimethyl sulfoxide, acetone, dimethylformamide; preferably wherein the nitrile is selected from acetonitrile, t- butylnitrile, and benzonitrile.

10. Compound of any one of claims 1 to 9, wherein the non-coordinating anion is selected from the group consisting of perchlorate [CICU]’, tetrafluoro borate [BF4]", hexafluoro phosphate [PFe]’, hexafluoro antimonate [SbFe]-, tetraphenyl borate [BPh4]“, tetrakis(trifluoromethyl)borate [B(CF3)4]“, tetrakis(pentafluorophenyl)borate [B(C6FS)4]_, tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate [B{(3,5-di-CF3)C6H3}4]“, and tetrakis(nonafluoro-t-butoxy)aluminate [AI{OC(CF3)3}4]“.11 . Compound of claim 1 , wherein the compound is characterized by formula[M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X945 to X968 and X979 to X954 except compound X973 of the following table:Catalyst M Ar NHC Z L A-X945 Mo 2,6-Me2Ph IMes PhO - BArFX946 Mo 2,6-Me2Ph IMes 2-CIPhO - BArFX948 Mo 2,6-Me2Ph IMes 2,6-CI2PhO - BArFX949 Mo 2,6-Me2Ph IMes 2,5-CI2PhO - BArFX950 Mo 2,6-Me2Ph IMes 3,5-CI2PhO - BArFX956 Mo 2,6-Me2Ph SIMes 2,6-CI2PhO - BArFX957 Mo 2,6-CI2Ph IMes 2,6-CI2PhO - BArFX970 Mo 3,5-Me2Ph IMes 2,6-CI2PhO ACN BArFX971 Mo 2,6-Me2Ph IMes 2,6-CI2PhO - BPh4X1041 Mo 2,6-Me2Ph IMes 2,6-CI2PhO ACN PF6X1042 Mo 2,6-Me2Ph IMes PhO - BF4X972 Mo 2,6-Me2Ph IMes 2,6-Br2PhO - BArFX712 Mo Ad IMes CeFsO ACN BArFX966 W 2,6-CI2Ph IMes 2,6-CI2PhO PivCN BArFX967 W 2,6-CI2Ph IMes CeFsO PivCN BArFX968 W 2,6-CI2Ph IMes PhO PivCN BArFX973 W 2,6-CI2Ph IMes HMTO PivCN BArFX979 W 2,6-CI2Ph IMes 2,6-Br2PhO PivCN BArFX965 W 3,5-Me2Ph IMes 2,6-CI2PhO PivCN BArFX977 W 3,5-Me2Ph IMes CeFsO PivCN BArFX980 W 3,5-Me2Ph IMes 2,6-Br2PhO PivCN BArFX954 W 3,5-Me2Ph IMes PhO PivCN BArF or compound of claim 2, wherein the compound is characterized by formula[M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)]A and wherein the compound is X973.

12. Compound of formula III[M(NHC)(X)(Y)(Z)(L)n]AmIII whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is triflate (TfO); or is halogenide selected from Cl- or Br-; or is -OR4, wherein R4is C1-10 alkyl or Ce-uaryl, respectively optionally substituted;L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br; n is 0, or 1 ;A is a non-coordinating anion; m is 0 or 1 ; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H; wherein in the compound of formula III(i) Z and L are TfO or Br, respectively, and n is 1 and m is 0; or(ii) Z is OR4and L is TfO or Br, and n is 1 and m is 0; or(iii) Z is TfO or Br, respectively, L is a neutral ligand, n is 0 or 1 and m is 1 ; and wherein the compound is characterized by formula[M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)] and wherein the compound is selected from compounds X359 to X944 of the following tables; or wherein the compound is characterized by formula[M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X930 to X963 of the following tables:Catalyst M Ar NHC L ZX359 Mo 2,6-Me2Ph IMes TfO TfOX793 Mo 2,6-Me2Ph SIMes TfO TfOX457 Mo 2,6-CI2Ph IMes TfO TfOX883 Mo 3,5-Me2Ph IMes TfO TfOX932 W 2,6-CI2Ph IMes Br BrX933 W 2,6-CI2Ph SIMes Br BrX959 W 3,5-Me2Ph IMes Br BrX942 Mo 2,6-Me2Ph IMes TfO PhOX943 Mo 2,6-Me2Ph IMes TfO 2-CIPhOX944 Mo 2,6-Me2Ph IMes TfO CeFsOCatalyst M Ar NHC Z L A-X930 Mo 2,6-Me2Ph IMes TfO - BArFX931 Mo 2,6-Me2Ph SIMes TfO - BArFX964 Mo 2,6-Me2Ph IMes TfO - BPh4X969 Mo 3,5-Me2Ph IMes TfO - BArFX955 Mo 2,6-CI2Ph IMes TfO - BArFX937 W 2,6-CI2Ph IMes Br PivCN BArFX963 W 3,5-Me2Ph IMes Br PivCN BArF3. Method of performing a metathesis reaction, comprising: reacting a compound as defined in any one of claims 1 to 11 with one or more olefins; or reacting a compound of formula III[M(NHC)(X)(Y)(Z)(L)n]AmIII whereinM is Mo or W;NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M; wherein NHC is defined in any one of claims 3 to 5;X is =NR1;Y is an alkylidene or arylidene =CR2R3;Z is triflate (TfO); or is halogenide selected from Cl- or Br-; or is -OR4, wherein R4is C1-10 alkyl or Ce-uaryl, respectively optionally substituted;L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br; n is 0 or 1 ;A is a non-coordinating anion; m is 0 or 1 ; whereinR1is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively;R2and R3are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R2and R3are H; wherein in the compound of formula III(iii) Z is TfO or Br, respectively, L is a neutral ligand, n is 0 or 1 and m is 1 ; preferably wherein the compound of formula III is characterized by formula[M(NHC)(=NAr)(=CHCMe2C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X930 to X963 , as defined in claim 12; with one or more olefins.

14. Method of claim 13, wherein the metathesis reaction is E-selective.

15. Use of a compound of one of the following formulae, or for an E-selective olefin metathesis reaction; or use of a compound of claim 12 as starting material or intermediate in the synthesis of a compound as defined in any one of claims 1 to 11 .

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