Complex with metal located in plane center of rotaxene as well as preparation method and application of complex

Abstract

The invention discloses a complex with metal located at the center of a rotaxene plane as well as a preparation method and application of the complex, and particularly relates to five types of novel complexes with metal located at the center of the rotaxene plane, in particular to five types of novel complexes with osmium located at the center of the rotaxene plane: [55753] osmium [15] rotaxene, [55735] osmium [15] rotaxene, [55663] osmium [15] rotaxene, [55636] osmium [15] rotaxene and [5555] osmium [15] rotaxene. The [55753] osmium [15] rotaxene 1a-1c can be prepared by respectively reacting P4a, P4b and P4c which are used as raw materials; the [55753] osmium [15] rotaxene 1d-1f can be prepared by a reaction of 1a-1c; [55735] osmium [15] rotaxene 2a-2c, [55663] osmium [15] rotaxene 3a and [55636] osmium [15] rotaxene 4a can be prepared from 1d-1f through different reactions; the [55555] osmium [15] rotaxene 5a-5c can be prepared by a reaction of 2a-2c; the [55555] osmium [15] rotaxene 5d-5f can be prepared by a reaction of 5a-5c; 5 g of [55555] osmium [15] rotaxene, 5 h, 5 i and 5 j can be prepared from 5 d through different reactions. The novel complex with the metal located in the plane center of the rotaxene can be used for catalyzing benzylamine oxidative coupling reaction to prepare imine, the reaction can be carried out in a room-temperature air atmosphere, the amount of the catalyst can be as low as 1 mol%, and the highest yield can reach 85% after 24 hours.

Description

Technical Field

[0001] The present invention relates to the fields of organic chemistry, coordination chemistry, metal organic chemistry and aromatic chemistry, and specifically to a complex in which a metal is located at the center of an annulare plane, in particular to the structure, preparation method and use of an osmium

[15] annulare complex. The complex includes five new skeletons:

[55753] osmium

[15] annulare,

[55735] osmium

[15] annulare,

[55663] osmium

[15] annulare,

[55636] osmium

[15] annulare and

[55555] osmium

[15] annulare, wherein the five numbers in the square brackets represent the number of atoms in each small ring in the complex, counting clockwise from the five-membered ring in the lower right corner, and the two numbers in the other square brackets represent the number of carbon atoms in the annulare. Background Art

[0002] Imines have high commercial value. Imines are important intermediates in the synthesis of many drugs, fine chemicals and bioactive substances. At the same time, imines are also widely used in various organic transformations, such as reduction, addition, cyclization and nitrogen heterocyclization reactions, etc. (ACS Catal. 2015, 5, 5851-5876) because they contain C=N double bonds. Traditionally, imines are generally prepared by condensation of amines and carbonyl compounds, especially unstable aldehydes, but this method usually requires the addition of dehydrating agents and Lewis acid catalysts, which will produce a lot of waste residues (Org. Lett. 2015, 17, 2442-2445). Therefore, from the perspective of green chemistry, it is very important to develop new methods for preparing imines.

[0003] The preparation of imines by photocatalytic oxidative coupling of two amine molecules is a relatively green method because it generally does not require the addition of other substances except the photocatalyst and the oxidant, so less waste residue is produced. In particular, when oxygen in the air can be used as an oxidant, the reaction can be carried out in the air without the addition of an additional oxidant, and the only by-product is water, which is economical and environmentally friendly (ACS Catal. 2015, 5, 5851-5876). To achieve this type of reaction, the most critical part is the design and preparation of the catalyst, so the synthesis of a mild and efficient catalyst is the goal pursued by scientists.

[0004] Metalloanol complexes such as ferrocene, half-sandwich complexes, and diphenylchromium are very important catalysts. They are widely used in various fields such as catalysis, materials, and biomedicine. The study of the coordination mode of metalloanol complexes has also revolutionized bonding theory and greatly promoted the development of coordination chemistry. Despite this, the metal atoms in all metalloanol complexes are outside the annular ring, and no complexes with the metal located in the annular plane have been reported. Summary of the invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a new type of osmium

[15] annulene complex with a metal located at the center of the annulene plane, and its preparation method and application. As a type of metal annulene complex with a novel structure, they should have good application prospects like complexes such as ferrocene in which the metal is located outside the annulene ring. And for the first time, a feasible method is provided for the preparation of such complexes, most of which are at room temperature and easy to operate. Considering the importance of amine oxidative coupling to prepare imines, the present invention applies five types of new osmium

[15] annulene complexes with a metal located at the center of the annulene plane to the catalytic process, and achieves good results.

[0006] To achieve the above object, the present invention uses the following technical solutions:

[0007] On the one hand, the present invention provides a novel complex in which a metal is located at the center of the annulare plane, which is a

[55753] metal

[15] annulare shown in formula (I), a

[55753] metal

[15] annulare shown in formula (I'), a

[55735] metal

[15] annulare shown in formula (II), a

[55663] metal

[15] annulare shown in formula (III), a

[55636] metal

[15] annulare shown in formula (IV) or a

[55555] metal

[15] annulare shown in formula (V), wherein the five numbers in the square brackets represent the number of atoms in each small ring in the complex, counting clockwise from the five-membered ring in the lower right corner, and the two numbers in the other square brackets represent the number of carbon atoms in the annulare:

[0008]

[0009] in,

[0010] M is Os or Ru;

[0011] [M] is M(PPh3)2, M(PEt3)2, M(CO)2, M(PhNC)2 or M(BuNC)2;

[0012] X is BPh4, F, Cl, Br or I;

[0013] Each R 1a and R 2aand -C(=O)-(C1-C6 alkyl), -C(=O)-(C1-C6 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkyl substituted with hydroxy, C3-C8 cycloalkyl, 3-8 membered heterocyclyl, C6-C 10 aryl or 5-10 membered heteroaryl; and

[0014] Each R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b and -C(=O)-(C1-C6 alkyl), -C(=O)-(C1-C6 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkyl substituted with hydroxy, C3-C8 cycloalkyl, 3-8 membered heterocyclyl, C6-C 10 Aryl or 5-10 membered heteroaryl.

[0015] In a preferred embodiment of the present invention,

[0016] Each R 1a and R 2a and -C(=O)-(C1-C4 alkyl), -C(=O)-(C1-C4 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkyl substituted with hydroxy, C3-C6 cycloalkyl, 3-6 membered heterocyclyl, C6-C10 aryl or 5-10 membered heteroaryl; and

[0017] Each R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b and -C(=O)-(C1-C4 alkyl), -C(=O)-(C1-C4 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkyl substituted with hydroxy, C3-C6 cycloalkyl, 3-6 membered heterocyclyl, C6-C 10 Aryl or 5-10 membered heteroaryl.

[0018] In a preferred embodiment of the present invention,

[0019] Each R 1a and R 2a are independently H, F, Cl, Br, I, -CN, -NO2, -NH2, -OH, -SH, -COOH, -C(=O)NH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)-CH3, -C(=O)-OCH3, p-toluenesulfonyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, allyl, propenyl, propargyl, propynyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propyloxy, isopropyl oxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, -OCH2CF2CHF2, methylthio, ethylthio, methylamino, dimethylamino, ethylamino, hydroxymethyl, 2-hydroxyethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, azetidinyl, pyrrolidinyl, tetrahydrofuranyl, piperidinyl, piperazinyl, morpholinyl, phenyl, indenyl, naphthyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzimidazolyl, indolyl, or quinolinyl; and

[0020] Each R 1b , R2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b are independently H, F, Cl, Br, I, -CN, -NO2, -NH2, -OH, -SH, -COOH, -C(=O)NH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)-CH3, -C(=O)-OCH3, p-toluenesulfonyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, allyl, propenyl, propargyl, propynyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propyloxy, isopropyl 1-Hydroxy, -OCHF, -OCF, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, -OCH2CF2CHF2, methylthio, ethylthio, methylamino, dimethylamino, ethylamino, hydroxymethyl, 2-hydroxyethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, azetidinyl, pyrrolidinyl, tetrahydrofuranyl, piperidinyl, piperazinyl, morpholinyl, phenyl, indenyl, naphthyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzimidazolyl, indolyl or quinolinyl.

[0021] In a preferred embodiment of the present invention, the complex of the present invention is

[55753] osmium

[15] annulene of formula (Ia),

[55753] osmium

[15] annulene of formula (I'-a),

[55735] osmium

[15] annulene of formula (II-a),

[55663] osmium

[15] annulene of formula (III-a),

[55636] osmium

[15] annulene of formula (IV-a) or

[55555] osmium

[15] annulene of formula (Va), wherein the five numbers in the square brackets represent the number of atoms in each small ring in the complex, counting clockwise from the five-membered ring in the lower right corner, and the two numbers in the other square brackets represent the number of carbon atoms in the annulene:

[0022]

[0023] in,

[0024] [Os] is [Os]', [Os]", [Os]"', [Os]"" or [Os]""';

[0025] [Os]' is Os(PPh3)2, [Os]" is Os(PEt3)2, [Os]"' is Os(CO)2, [Os]"" is Os(PhNC)2, [Os]""' is Os(BuNC)2;

[0026] X, R 1a , R 2a , R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b Has the definition as described in the present invention.

[0027] In a preferred embodiment of the present invention, the

[55753] osmium

[15] annulene represented by formula (I'-a) is selected from the

[55753] osmium

[15] annulene represented by formula (I'-a-1):

[0028]

[0029] Among them, [Os] and R 1a Has the definition as described in the present invention.

[0030] In a preferred embodiment of the present invention, the

[55735] osmium

[15] annulene represented by formula (II-a) is selected from the

[55735] osmium

[15] annulene represented by formula (II-a-1):

[0031]

[0032] Among them, [Os]', R 1a and R 2a Has the definition as described in the present invention.

[0033] In a preferred embodiment of the present invention, the

[55555] osmium

[15] annulene represented by formula (Va) is selected from the

[55555] osmium

[15] annulene represented by formula (Va-1), the

[55555] osmium

[15] annulene represented by formula (Va-2) or the

[55555] osmium

[15] annulene represented by formula (Va-3):

[0034]

[0035] Among them, [Os]', [Os]”, R 1a and R 2a Has the definition as described in the present invention.

[0036] In a preferred embodiment of the present invention, the complex of the present invention is a complex having one of the following structures:

[0037]

[0038]

[0039] wherein [Os]′ and [Os]” have the meanings as described in the present invention.

[0040] On the other hand, the present invention provides a method for preparing

[55753] osmium

[15] annulene represented by formula (Ia), comprising the following steps: under inert gas conditions, reacting a compound represented by formula (I-a1) with a compound heating the reaction in an organic solvent, and after the reaction is completed, separating and purifying to obtain

[55753] osmium

[15] annulene represented by formula (Ia);

[0041]

[0042] Among them, [Os], X, R 1a and R 2a Has the definition as described in the present invention.

[0043] In a preferred embodiment of the present invention, the method for preparing the

[55753] osmium

[15] annulene of formula (Ia) of the present invention comprises:

[0044] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0045] The organic solvent is 1,2-dichloroethane, dichloromethane, chloroform, tetrahydrofuran, methanol or toluene;

[0046] The reaction temperature is 40-80°C, preferably 40-60°C, more preferably 50°C, 55°C;

[0047] The reaction time is 8-18 hours, preferably 10-16 hours, more preferably 12 hours, 15 hours;

[0048] The compound represented by formula (I-a1) and the compound The molar ratio is 1:2-10, preferably 1:3-9, more preferably 1:4, 1:8.

[0049] In another aspect, the present invention provides a method for preparing

[55753] osmium

[15] annulene of formula (I'-a), comprising the following steps: dissolving

[55753] osmium

[15] annulene of formula (Ia) in an organic solvent under inert gas conditions, adding KOH and reacting at room temperature, and after the reaction is completed, separating and purifying to obtain

[55753] osmium

[15] annulene of formula (I'-a);

[0050]

[0051] Among them, [Os], X, R 1a and R 2a Has the definition as described in the present invention.

[0052] In a preferred embodiment of the present invention, the method for preparing the

[55753] osmium

[15] annulene of formula (I'-a) of the present invention comprises:

[0053] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0054] The organic solvent is 1,2-dichloroethane, methanol, dichloromethane, chloroform, tetrahydrofuran or toluene;

[0055] The room temperature is 5-35°C, preferably 25-35°C;

[0056] The reaction time is 1-6 hours, preferably 1-3 hours, more preferably 2 hours;

[0057] The molar ratio of

[55753] osmium

[15] annulene represented by formula (Ia) to KOH is 1:10 to 40, preferably 1:20 to 30, and more preferably 1:25.

[0058] In another aspect, the present invention provides a method for preparing

[55735] osmium

[15] annulene of formula (II-a), comprising the following steps: dissolving

[55753] osmium

[15] annulene of formula (I'-a) in an organic solvent under room temperature and air conditions, adding AlCl3 and Al2O3 and reacting at room temperature, and after the reaction is completed, separating and purifying to obtain

[55735] osmium

[15] annulene of formula (II-a);

[0059]

[0060] Among them, [Os], R 1a and R 2a Has the definition as described in the present invention.

[0061] In a preferred embodiment of the present invention, the method for preparing the

[55735] osmium

[15] annulene of formula (II-a) of the present invention comprises:

[0062] The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0063] The room temperature is 5-35°C, preferably 25-35°C;

[0064] The reaction time is 8-18 hours, preferably 10-16 hours, more preferably 12 hours;

[0065] The molar ratio of

[55753] osmium

[15] annulene represented by formula (I'-a) to AlCl3 is 1:5 to 15, preferably 1:8 to 12, and more preferably 1:10;

[0066] The molar ratio of AlCl3 to Al2O3 is 1:10 to 20, preferably 1:16 to 20, and more preferably 1:18.

[0067] In another aspect, the present invention provides a method for preparing

[55663] osmium

[15] annulene of formula (III-a), comprising the following steps: dissolving

[55753] osmium

[15] annulene of formula (I'-a) in an organic solvent under inert gas conditions and heating the mixture for reaction, and after the reaction is completed, separating and purifying the mixture to obtain

[55663] osmium

[15] annulene of formula (III-a);

[0068]

[0069] Among them, [Os], R 1a and R 2a Has the definition as described in the present invention.

[0070] In a preferred embodiment of the present invention, the method for preparing the

[55663] osmium

[15] annulene of formula (III-a) of the present invention comprises:

[0071] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0072] The organic solvent is tetrahydrofuran, dichloromethane, chloroform, 1,2-dichloroethane, methanol or toluene;

[0073] The reaction temperature is 50-100°C, preferably 70-90°C, more preferably 80°C;

[0074] The reaction time is 60-120 hours, preferably 80-100 hours, more preferably 96 hours.

[0075] In another aspect, the present invention provides a method for preparing

[55636] osmium

[15] annulene of formula (IV-a), comprising the following steps: under inert gas conditions, dissolving

[55753] osmium

[15] annulene of formula (I'-a-1) of the present invention and 1-chloro-1,3-dihydro-3,3-dimethyl-1,2-benzoiodine in an organic solvent for reaction at room temperature, and after the reaction is completed, separating and purifying to obtain

[55636] osmium

[15] annulene of formula (IV-a);

[0076]

[0077] Among them, [Os] and R 1a Has the definition as described in the present invention.

[0078] In a preferred embodiment of the present invention, the method for preparing the

[55636] osmium

[15] annulene of formula (IV-a) of the present invention comprises:

[0079] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0080] The organic solvent is 1,2-dichloroethane, dichloromethane, chloroform, tetrahydrofuran, methanol or toluene;

[0081] The room temperature is 5-35°C, preferably 25-35°C;

[0082] The reaction time is 8-18 hours, preferably 10-16 hours, more preferably 12 hours;

[0083] The molar ratio of

[55753] osmium

[15] annulene represented by formula (I'-a-1) to 1-chloro-1,3-dihydro-3,3-dimethyl-1,2-benzoiodooxolane is 1:1 to 5, preferably 1:1 to 3, and more preferably 1:1.5.

[0084] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene represented by formula (Va-1), comprising the following steps: dissolving

[55735] osmium

[15] annulene represented by formula (II-a-1) of the present invention in an organic solvent under inert gas conditions, adding an acid to the solution to react at room temperature, and after the reaction is completed, separating and purifying to obtain

[55555] osmium

[15] annulene represented by formula (Va-1);

[0085]

[0086] Among them, [Os]', R 1a and R 2a Has the definition as described in the present invention.

[0087] In a preferred embodiment of the present invention, the method for preparing the

[55555] osmium

[15] annulene represented by formula (Va-1) of the present invention comprises:

[0088] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0089] The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0090] The acid is hydrochloric acid, tetrafluoroboric acid, hexafluorophosphoric acid or perchloric acid;

[0091] The room temperature is 5-35°C, preferably 25-35°C;

[0092] The reaction time is 8-18 hours, preferably 10-16 hours, more preferably 12 hours;

[0093] The molar ratio of

[55735] osmium

[15] annulene represented by formula (II-a-1) to the acid is 1:20 to 60, preferably 1:30 to 50, and more preferably 1:40.

[0094] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene represented by formula (Va-2), comprising the following steps: dissolving the

[55555] osmium

[15] annulene represented by formula (Va-1) of the present invention in an organic solvent under inert gas conditions, adding t-BuLi to the solution at low temperature, adding methanol to the solution after the reaction is completed to quench the reaction, and then separating and purifying to obtain the

[55555] osmium

[15] annulene represented by formula (Va-2);

[0095]

[0096] Among them, [Os]', R 1a and R 2a Has the definition as described in the present invention.

[0097] In a preferred embodiment of the present invention, the method for preparing the

[55555] osmium

[15] annulene represented by formula (Va-2) of the present invention comprises:

[0098] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0099] The organic solvent is tetrahydrofuran, dichloromethane, chloroform, 1,2-dichloroethane, methanol or toluene;

[0100] The reaction temperature is -10 to -60°C, preferably -30 to -50°C, more preferably -40°C;

[0101] The reaction time is 5-60 minutes, preferably 10-30 minutes, more preferably 20 minutes;

[0102] The molar ratio of

[55555] osmium

[15] annulene represented by formula (Va-1) to t-BuLi is 1:3 to 10, preferably 1:5 to 7, and more preferably 1:6.

[0103] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene of formula (Va-3), comprising the following steps: dissolving the

[55555] osmium

[15] annulene of formula (Va-2) of the present invention in an organic solvent under inert gas conditions, adding PEt3 to the solution, heating the solution for reaction, and separating and purifying after the reaction to obtain the

[55555] osmium

[15] annulene of formula (Va-3);

[0104]

[0105] Among them, [Os]', [Os]”, R 1a and R 2a Has the definition as described in the present invention.

[0106] In a preferred embodiment of the present invention, the method for preparing the

[55555] osmium

[15] annulene represented by formula (Va-3) of the present invention comprises:

[0107] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0108] The organic solvent is 1,2-dichlorobenzene or diethylene glycol dimethyl ether;

[0109] The reaction temperature is 150-250°C, preferably 170-190°C, more preferably 180°C;

[0110] The reaction time is 24-48 hours, preferably 30-40 hours, more preferably 36 hours;

[0111] The molar ratio of

[55555] osmium

[15] annulene represented by formula (Va-2) to PEt3 is 1:5 to 15, preferably 1:8 to 12, and more preferably 1:10.

[0112] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene 5h, comprising the following steps: dissolving

[55555] osmium

[15] annulene 5d in an organic solvent under an inert gas condition, adding ICl to the solution, reacting at room temperature, and separating and purifying to obtain

[55555] osmium

[15] annulene 5h after the reaction is completed;

[0113]

[0114] Wherein, [Os]' is Os(PPh3)2.

[0115] In a preferred embodiment of the present invention, the method for preparing

[55555] osmium

[15] annulene 5h of the present invention comprises:

[0116] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0117] The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0118] The room temperature is 5-35°C, preferably 25-35°C;

[0119] The reaction time is 6-24 hours, preferably 10-15 hours, more preferably 12 hours;

[0120]

[55555] The molar ratio of osmium

[15] annulene 5d to ICl is 1:5 to 15, preferably 1:8 to 12, and more preferably 1:10.

[0121] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene 5i, comprising the following steps: dissolving

[55555] osmium

[15] annulene 5d in an organic solvent under an inert gas condition, adding NO2BF4 or t-BuONO to the solution, reacting at room temperature, and separating and purifying to obtain

[55555] osmium

[15] annulene 5i after the reaction is completed;

[0122]

[0123] Wherein, [Os]' is Os(PPh3)2.

[0124] In a preferred embodiment of the present invention, the method for preparing

[55555] osmium

[15] annulene 5i of the present invention comprises:

[0125] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0126] The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0127] The room temperature is 5-35°C, preferably 25-35°C;

[0128] The reaction time is 6-24 hours, preferably 10-15 hours, more preferably 12 hours;

[0129]

[55555] The molar ratio of osmium

[15] annulene 5d to NO2BF4 or t-BuONO is 1:1 to 6, preferably 1:2 to 4, and more preferably 1:3.

[0130] In another aspect, the present invention provides a method for preparing

[55555] osmium

[15] annulene 5j, comprising the following steps: dissolving

[55555] osmium

[15] annulene 5d in an organic solvent under an inert gas condition, adding t-BuOCl to the solution, heating the solution for reaction, and separating and purifying after the reaction to obtain

[55555] osmium

[15] annulene 5j;

[0131]

[0132] Wherein, [Os]' is Os(PPh3)2.

[0133] In a preferred embodiment of the present invention, the method for preparing

[55555] osmium

[15] annulene 5j of the present invention comprises:

[0134] The inert gas is helium, neon, argon, krypton, xenon or radon;

[0135] The organic solvent is chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0136] The reaction temperature is 30-60°C, preferably 35-50°C, more preferably 42°C;

[0137] The reaction time is 6-24 hours, preferably 10-15 hours, more preferably 12 hours;

[0138] The molar ratio of

[55555] osmium

[15] annulene 5d to t-BuOCl is 1:60 to 180, preferably 1:80 to 120, and more preferably 1:100.

[0139] In another aspect, the present invention provides a novel metal complex located at the center of the annulene plane for use in catalyzing the oxidative coupling reaction of benzylamine to prepare imines.

[0140] In a preferred embodiment of the present invention, the application of the present invention comprises the following steps: under air atmosphere, the novel metal complex located at the center of the annulene plane, benzylamine and an organic solvent are added to a reactor together, and light is irradiated to react at room temperature to obtain the product (E)-N-benzyl-1-phenylmethylamine, and the reaction formula is as follows:

[0141]

[0142] In a preferred embodiment of the present invention, the application of the present invention, wherein:

[0143] The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene;

[0144] The room temperature is 5-35°C, preferably 25-35°C;

[0145] The illumination is blue light illumination, preferably a blue light LED lamp with an emission wavelength of 450-455nm and a power of 40 watts;

[0146] The reaction time is 12-48 hours, preferably 20-30 hours, more preferably 24 hours;

[0147] The molar ratio of the novel metal complex located at the center of the annulene plane to benzylamine is 0.005-0.05:1, preferably 0.005-0.02:1, and more preferably 0.01:1.

[0148] Compared with the prior art, the present invention has the following beneficial effects:

[0149] (1) For the first time, an osmium

[15] annulene complex with the metal located at the center of the annulene plane was reported. The complex has a novel structure and provides a feasible method for the preparation of this type of complex. Most reactions are performed at room temperature and the operation is simple.

[0150] (2) Osmium

[15] annulene complexes with the metal located at the center of the annulene plane have the following advantages in catalyzing the oxidative coupling reaction of benzylamine to prepare imines:

[0151] a. High catalytic efficiency and low catalyst dosage, only 1 mol% of catalyst is needed;

[0152] b. The catalytic reaction is specific, with few side reactions and high yield;

[0153] c. The reaction takes place at room temperature and the catalytic conditions are mild.

[0154] Definitions and general terms

[0155] Certain embodiments of the present invention are now described in detail, examples of which are illustrated by the accompanying structural formulas and chemical formulae. The present invention is intended to encompass all substitutions, modifications, and equivalent technical solutions, which are all included within the scope of the present invention as defined in the claims. It should be appreciated by those skilled in the art that many methods and materials similar or equivalent to those described herein can be used to practice the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the combined documents, patents, and similar materials differ from or contradict the present application (including but not limited to defined terms, term applications, described technologies, etc.), the present application shall prevail.

[0156] It should be further appreciated that certain features of the invention, which for clarity are described in multiple separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which for brevity are described in a single embodiment, may also be provided separately or in any suitable sub-combination.

[0157] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0158] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0159] The term "optionally substituted by..." can be used interchangeably with the term "unsubstituted or substituted by...", that is, the structure is unsubstituted or substituted by one or more substituents described in the present invention, and the substituents described in the present invention include, but are not limited to D, F, Cl, Br, I, N3, -CN, -NO2, -NH2, -OH, -SH, -COOH, -CONH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)-alkyl, -C(=O)-alkoxy, p-toluenesulfonyl, trimethylsilyl, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, hydroxy-substituted alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, etc.

[0160] In general, the term "substituted" means that one or more hydrogen atoms in a given structure or group are replaced by a specific substituent. Unless otherwise indicated, a substituent can be substituted at each reasonable position of the group. When more than one position in the given structural formula can be substituted by one or more specific substituents selected, the substituent can be substituted at each reasonable position in the structural formula in the same or different manner.

[0161] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present invention, "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0162] In various parts of this specification, the substituents of the disclosed compounds of the present invention are disclosed according to group types or ranges. It is particularly noted that the present invention includes each independent secondary combination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" specifically refers to the independently disclosed methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl.

[0163] In various parts of the present invention, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood as a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents an alkylene group or an arylene group, respectively, that is linked.

[0164] The terms "halogen" and "halo" are used interchangeably herein to refer to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0165] The term "heteroatom" refers to O, S, N, P and Si, including any oxidation state of N, S and P; in the form of primary, secondary, tertiary amines and quaternary ammonium salts; or in the form of a substituted hydrogen on a nitrogen atom in a heterocyclic ring, for example, N (such as N in 3,4-dihydro-2H-pyrrolyl), NH (such as NH in pyrrolidinyl) or NR (such as NR in N-substituted pyrrolidinyl, R is a substituent described in the present invention).

[0166] The term "alkyl" or "alkyl group" as used herein refers to a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkyl group contains 1 to 6 carbon atoms; in another embodiment, the alkyl group contains 1 to 4 carbon atoms; in another embodiment, the alkyl group contains 1 to 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -C(CH3)3), and the like.

[0167] The term "alkenyl" refers to a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms and having at least one site of unsaturation, i.e., a carbon-carbon sp 2Double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including "cis" and "trans" orientations, or "E" and "Z" orientations. In one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2-6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), 1-propenyl (i.e., propenyl, -CH=CH-CH3), and the like.

[0168] The term "alkynyl" refers to a straight or branched monovalent hydrocarbon radical containing 2-12 carbon atoms, wherein there is at least one site of unsaturation, i.e., a carbon-carbon sp triple bond, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2-6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl (-C≡CH), propargyl (-CH2C≡CH), 1-propynyl (i.e., propynyl, -C≡C-CH3), and the like.

[0169] The term "alkoxy" means an alkyl group attached to the rest of the molecule via an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-6 carbon atoms; in another embodiment, the alkoxy group contains 1-4 carbon atoms; in yet another embodiment, the alkoxy group contains 1-3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents as described herein.

[0170] Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-propyloxy, n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (isopropyloxy, i-PrO, i-propoxy, -OCH(CH3)2), 1-butoxy (n-BuO, n-butoxy, -OCH2CH2CH2CH3), 2-methyl-1-propoxy (i-BuO, i-butoxy, -OCH2CH(CH3)2), 2-butoxy (s-BuO, s-butoxy, -OCH(CH3)CH2CH3), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH3)3), and the like.

[0171] The term "alkylthio" means an alkyl group attached to the rest of the molecule via a sulfur atom, wherein the alkyl group has a meaning as described herein. Unless otherwise specified, the alkylthio group contains 1-12 carbon atoms. In one embodiment, the alkylthio group contains 1-6 carbon atoms; in another embodiment, the alkylthio group contains 1-4 carbon atoms; in yet another embodiment, the alkylthio group contains 1-3 carbon atoms. The alkylthio group may be optionally substituted with one or more substituents as described herein.

[0172] Examples of alkylthio groups include, but are not limited to, methylthio (MeS, -SCH3), ethylthio (EtS, -SCH2CH3), 1-propylthio (n-PrS, n-propylthio, -SCH2CH2CH3), 2-propylthio (i-PrS, i-propylthio, -SCH(CH3)2), 1-butylthio (n-BuS, n-butylthio, -SCH2CH2CH2CH3), 2-methyl-1-propylthio (i-BuS, i-butylthio, -SCH2CH(CH3)2), 2-butylthio (s-BuS, s-butylthio, -SCH(CH3)CH2CH3), 2-methyl-2-propylthio (t-BuS, t-butylthio, -SC(CH3)3), and the like.

[0173] The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N,N-dialkylamino", wherein the amino group is independently substituted with one or two alkyl groups, wherein the alkyl groups have the meanings as described herein. Suitable alkylamino groups can be monoalkylamino or dialkylamino, such examples include, but are not limited to, N-methylamino (methylamino), N-ethylamino (ethylamino), N,N-dimethylamino (dimethylamino), N,N-diethylamino (diethylamino) and the like. The alkylamino group is optionally substituted with one or more substituents described herein.

[0174] The term "hydroxy-substituted alkyl" means an alkyl group substituted with one or more hydroxy groups, wherein the alkyl group has the meaning as described herein; such examples include, but are not limited to, hydroxymethyl, 2-hydroxyethyl, 2-hydroxy-1-propyl, 3-hydroxy-1-propyl, 2,3-dihydroxypropyl and the like.

[0175] The term "haloalkyl" means that an alkyl group is substituted by one or more halogen atoms, wherein the alkyl group has the meaning as described herein, such examples include, but are not limited to, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CHF2, -CH2CF3, -CHFCH3, -CH2CH2F, -CF2CH3, -CH2CF2CHF2, etc. In one embodiment, C1-C6 haloalkyl comprises fluorine-substituted C1-C6 alkyl; in another embodiment, C1-C4 haloalkyl comprises fluorine-substituted C1-C4 alkyl; in yet another embodiment, C1-C2 haloalkyl comprises fluorine-substituted C1-C2 alkyl.

[0176] The term "haloalkoxy" means that an alkoxy group is substituted by one or more halogen atoms, wherein the alkoxy group has the meaning as described in the present invention, such examples include, but are not limited to, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CHF2, -OCH2CF3, -OCHFCH3, -OCH2CH2F, -OCF2CH3, -OCH2CF2CHF2, etc. In one embodiment, C1-C6 haloalkoxy comprises fluorine-substituted C1-C6 alkoxy; in another embodiment, C1-C4 haloalkoxy comprises fluorine-substituted C1-C4 alkoxy; in yet another embodiment, C1-C2 haloalkoxy comprises fluorine-substituted C1-C2 alkoxy.

[0177] The term "jk-membered", where j and k are integers greater than 0 and k is greater than j, typically describes the number of ring atoms in the molecule. For example, 5-10 membered heteroaryl means a heteroaryl consisting of 5, 6, 7, 8, 9 or 10 ring atoms. For another example, pyridinyl is a 6-membered heteroaryl, and piperidinyl is a 6-membered heterocyclyl.

[0178] The term "cycloalkyl" means a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms. Bicyclic or tricyclic ring systems can include fused rings, bridged rings and spiro rings. In one embodiment, the cycloalkyl contains 3-10 carbon atoms; in another embodiment, the cycloalkyl contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl contains 3-6 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The cycloalkyl group is optionally substituted with one or more substituents described herein.

[0179] The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a non-aromatic, saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 ring atoms, wherein the bicyclic or tricyclic ring system may include fused rings, bridged rings and spiro rings. One or more atoms in the ring are independently replaced by heteroatoms, and the heteroatoms have the meanings as described herein. In one embodiment, heterocyclyl is a monocyclic heterocyclyl consisting of 3-8 ring atoms (2-6 carbon atoms and 1-3 heteroatoms selected from N, O, P, S, where S or P is optionally substituted by one or more oxygen atoms to give groups like SO, SO2, PO, PO2); in another embodiment, heterocyclyl is a monocyclic heterocyclyl consisting of 3-6 ring atoms (2-5 carbon atoms and 1-3 heteroatoms selected from N, O, P, S, where S or P is optionally substituted by one or more oxygen atoms to give groups like SO, SO2, PO, PO2); in another embodiment, heterocyclyl is a bicyclic heterocyclyl consisting of 7-12 ring atoms (4-9 carbon atoms and 1-3 heteroatoms selected from N, O, P, S, where S or P is optionally substituted by one or more oxygen atoms to give groups like SO, SO2, PO, PO2). The heterocyclyl groups are optionally substituted by one or more substituents described herein.

[0180] The heterocyclic group can be a carbon group or a heteroatom group, wherein the -CH2- group of the ring is optionally replaced by -C(=O)-, the sulfur atom of the ring is optionally oxidized to an S-oxide, and the nitrogen atom of the ring is optionally oxidized to an N-oxygen compound. Examples of heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, 2-pyrrolinyl, 3-pyrrolinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, 1,3-dioxolane, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, oxazepine Base, diazepine Base, thiazolin Examples of heterocyclic groups in which the -CH2- group is replaced by -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidinyl, 3,5-dioxopiperidinyl, pyrimidinedione, and the like. Examples of heterocyclic groups in which the sulfur atom is oxidized include, but are not limited to, sulfolane, thiomorpholinyl 1,1-dioxide, and the like. The heterocyclic group is optionally substituted by one or more substituents described herein.

[0181] The term "aryl" refers to a monocyclic, bicyclic and tricyclic carbon ring system containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic, and wherein each ring system contains a ring consisting of 3-7 atoms. The aryl group is usually, but not necessarily, connected to the parent molecule through the aromatic ring of the aryl group. The term "aryl" can be used interchangeably with the term "aromatic ring" or "aromatic ring". Examples of aryl groups can include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted by one or more substituents described in the present invention.

[0182] The term "heteroaryl" refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring consisting of 5-7 atoms. The heteroaryl group is usually, but not necessarily, connected to the parent molecule through the aromatic ring of the heteroaryl group. The term "heteroaryl" can be used interchangeably with the terms "heteroaromatic ring", "aromatic heterocycle" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, the 5-10 atom heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.

[0183] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl , 1,2,3-thiodiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl; also includes the following bicyclic rings, but is by no means limited to these bicyclic rings: benzimidazolyl, benzofuranyl, benzothiophenyl, indolyl (such as 2-indolyl), purinyl, quinolyl (such as 2-quinolyl, 3-quinolyl, 4-quinolyl), isoquinolyl (such as 1-isoquinolyl), [1,2,4]triazolo[4,3-b]pyridazinyl, [1,2,4]triazolo[1,5-a]pyrimidinyl, [1,2,4]triazolo[1,5-a]pyridinyl, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0184] Figure 1 This is the X-ray single crystal structure of the

[55753] osmium

[15] annulene complex 1c (in order to make the crystal structure clearer, the phenyl groups on the three P atoms P1, P2 and P3 are deleted).

[0185] Figure 2 This is the X-ray single crystal structure of the

[55753] osmium

[15] annulene complex 1d (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0186] Figure 3 This is the X-ray single crystal structure of

[55735] osmium

[15] annulene complex 2b (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0187] Figure 4 This is the X-ray single crystal structure of the

[55663] osmium

[15] annulene complex 3a (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0188] Figure 5 This is the X-ray single crystal structure of the

[55636] osmium

[15] annulene complex 4a (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0189] Figure 6 This is the X-ray single crystal structure of the

[55555] osmium

[15] annulene complex 5a (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0190] Figure 7 This is the X-ray single crystal structure of the

[55555] osmium

[15] annulene complex 5d (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0191] Figure 8 This is the X-ray single crystal structure of

[55555] osmium

[15] annulene complex 5h (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0192] Fig. 9 This is the X-ray single crystal structure of the

[55555] osmium

[15] annulene complex 5i (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0193] Fig.10 This is the X-ray single crystal structure of the

[55555] osmium

[15] annulene complex 5j (in order to make the crystal structure clearer, the phenyl groups on the two P atoms P1 and P2 are deleted).

[0194] Fig.11 For complex P3a 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0195] Fig.12 For complex P4a 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0196] Fig.13 For complex P3c 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0197] Fig.14 For the complex P4c 1 H NMR (600 MHz, CDCl3) spectrum.

[0198] Fig.15

[55753] Osm

[15] annulene 1a 1 H NMR (400 MHz, CDCl3) spectrum.

[0199] Fig.16

[55753] Osmium

[15] annulene 1b 1 H NMR (600 MHz, CDCl3) spectrum.

[0200] Fig.17

[55753] Osm

[15] annulene 1c 1 H NMR (400 MHz, CD2Cl2) spectrum.

[0201] Fig.18

[55753] osmium

[15] annulene 1d 1 H NMR (600 MHz, CDCl3) spectrum.

[0202] Fig.19

[55753] osmium

[15] annulene 1e 1 H NMR (600 MHz, CDCl3) spectrum.

[0203] Fig. 20

[55753] osmium

[15] annulene 1f 1 H NMR (600 MHz, CDCl3) spectrum.

[0204] Fig.21

[55735] Osm

[15] annulene 2a 1 H NMR (600 MHz, CDCl3) spectrum.

[0205] Fig. 22

[55735] Osmium

[15] annulene 2b 1 H NMR (400 MHz, CDCl3) spectrum.

[0206] Fig.23

[55735] Osmium

[15] annulene 2c 1 H NMR (600 MHz, CDCl3) spectrum.

[0207] Fig.24

[55663] Osmium

[15] annulene 3a 1 H NMR (600 MHz, CDCl3) spectrum.

[0208] Fig.25

[55636] Osmium

[15] annulene 4a 1 H NMR (600 MHz, CDCl3) spectrum.

[0209] Fig.26

[55555] osmium

[15] annulene 5a 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0210] Fig. 27

[55555] osmium

[15] annulene 5b 1 H NMR (400 MHz, CDCl3) spectrum.

[0211] Fig.28

[55555] osmium

[15] annulene 5c 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0212] Fig.29

[55555] osmium

[15] annulene 5d 1 H NMR (850 MHz, 1,1,2,2-tetrachloroethane-d2) spectrum.

[0213] Fig.30

[55555] osmium

[15] annulene 5e 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0214] Fig.31

[55555] osmium

[15] annulene 5f 1 H NMR (600 MHz, CD2Cl2) spectrum.

[0215] Fig.32

[55555] osmium

[15] annulene 5g 1 H NMR (400 MHz, CDCl3) spectrum.

[0216] Fig.33

[55555] osmium

[15] annulene 5h 1 H NMR (600 MHz, CDCl3) spectrum.

[0217] Fig.34

[55555] osmium

[15] annulene 5i 1 H NMR (600 MHz, CDCl3) spectrum.

[0218] Fig.35

[55555] osmium

[15] annulene 5j 1 H NMR (600 MHz, CDCl3) spectrum.

[0219] The above spectra were all detected using conventional detection methods and conditions in the art. DETAILED DESCRIPTION

[0220] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation of the present invention. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concepts of the present disclosure. Such structures and technologies are also described in many publications.

[0221] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0222] Example 1: Synthesis of

[55753] Osmium

[15] annulene 1a

[0223]

[0224] Step 1) Synthesis of compound P2a

[0225] Complex P1a was synthesized according to existing literature (Nat. Commun. 2024, 14, 4378.). At room temperature, in an argon atmosphere, complex P1a (200 mg, 0.16 mmol) and LiAlH4 (25 mg, 0.66 mmol) were added successively to a mixed solvent of dichloromethane / ether (5 mL, volume ratio (V / V) = 1 / 1) and stirred at room temperature for 5 minutes. Then, it was filtered in an argon atmosphere, the filtrate was decompressed to remove the solvent, the remaining solid was dissolved in methanol (5 mL), and then a methanol (2 mL) solution of NaBPh4 (140 mg, 0.41 mmol) was added. After 1 minute, it was filtered, and the solid precipitate was washed with methanol (3 mL×3), and then dissolved in dichloromethane (3 mL). n-Hexane (30 mL) was dropped into the solution, and the precipitate was collected by filtration, washed with n-hexane (5 mL×3), and dried to obtain a green solid compound P2a.

[0226] Step 2) Synthesis of compound P3a

[0227] The obtained P2a was dissolved in dichloromethane (5 mL), and then p-toluenesulfonyl chloride (153 mg, 0.8 mmol) was added. After the solution was reacted at 35°C for 12 hours, it was filtered through diatomaceous earth, and the filtrate was vacuum concentrated to about 2 ml, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as the eluent to obtain a green solid compound P3a (105 mg, yield 40%). The structure of compound P3a was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0228] 1 H NMR(600MHz,CD2Cl2,ppm)δ:7.62(br,1H,C5H),7.49(d,J(HH)=4.1Hz,1H,C6H),7.24(d,J(HH)=8.2Hz,1H,C8 H),7.18(br,1H,C3H),6.56(t,J(HH)=8.2Hz,1H,C9H),5.85(d,J(HH)=8.2Hz,1H,C10H),2.39(s,3H,CH3)and 7.81-6.70(69H, other aromaticprotons).

[0229] 31 P{ 1 H}NMR (243MHz, CD2Cl2, ppm) δ: 6.19 (t, J (PP) = 6.8Hz, CPPh3), -5.02 (d, J (PP) = 6.8Hz, OsPPh3).

[0230] 13 C{ 1 H}NMR (151MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:323.5(td,J(PC)=15.7Hz,J(PC)=10.9Hz,C1),224.5(t,J(PC)=10.9H z,C7),199.8(t,J(PC)=12.3Hz,C11),191.1(d,J(PC)=29.2Hz,C4),160.6(t,J(PC )=4.9Hz,C6),160.0(s,C5),144.1(d,J(PC)=17.5Hz,C3),139.3(s,C9),136.9(s, C8),133.8(br,C10),128.3(td,J(PC)=89.8Hz,J(PC)=6.0Hz,C2),21.8(s,CH3)and 143.6-121.4(otheraromatic carbon atoms).

[0231] HRMS(ESI):(m / z)calcd for P3a[C 72 H58 O2OsP3S] + 1271.2980, found 1271.2957.

[0232] Step 3) Synthesis of compound P4a

[0233] In an argon atmosphere, P3a (200 mg, 0.12 mmol) and trimethylsilylethynyl lithium (50 mg, 0.48 mmol) were dissolved in tetrahydrofuran (10 mL) and reacted at room temperature for 10 minutes. After the solution was vacuum-evacuated, the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation (eluent: dichloromethane) to obtain a red solid compound P4a (115.6 mg, yield 60%). The structure of compound P4a was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0234] 1 H NMR (600MHz, CD2Cl2, ppm) δ: 7.46 (d, J (HH) = 4.1Hz, 1H, C5H), 7.30 (d, J (HH) = 4.1Hz, 1H, C6H), 7. 22(br,1H,C8H),6.94(br,1H,C3H),5.57(s,1H,C10H),2.30(s,3H,C13H),1.69(s,3H,C12H),and 7.71-6.77(69H, other aromatic protons).

[0235] 31 P{ 1 H}NMR (243MHz, CD2Cl2, ppm) δ: 5.80 (t, J (PP) = 7.9 Hz, CPPh3), -3.65 (d, J (PP) = 7.9 Hz, OsPPh3).

[0236] 13 C{ 1 H}NMR (151MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13C HMBC,ppm)δ:323.3(td,J(PC)=16.4,J(PC)=11.2Hz,C1),226.2(t,J(PC)=11.1Hz,C 7),200.3(t,J(PC)=12.1Hz,C11),188.1(d,J(PC)=30.0Hz,C4),164.6-163.6(BPh4 ,αC),159.6(s,C5),159.7(s,C6),151.4(t,J(PC)=3.1Hz,C9),142.3(m,C3),137.3 (s,C10),135.7(s,C8),121.4(d,J(PC)=90.6Hz,C2),26.1(s,C12),21.3(s,C13)and 143.2-121.4(otheraromatic carbon atoms).

[0237] HRMS(ESI):(m / z)calcd for P4a[C 73 H 60 O2OsP3S] + 1285.3137, found 1285.3129.

[0238] Step 4) Synthesis of

[55753] Osmium

[15] annulene 1a

[0239] In an argon atmosphere, P4a (200 mg, 0.13 mmol) and p-toluenesulfonylacetylene (182 mg, 1.04 mmol) were dissolved in 1,2-dichloroethane (5 mL) and reacted at 50°C for 15 hours. After the solution was vacuum-evacuated, the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation (eluent: dichloromethane) to obtain a red solid compound 1a (44.7 mg, yield 20%). The structure of compound 1a was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0240] 1H NMR(400MHz,CDCl3,ppm)δ:9.54(dd,J(HH)=8.7Hz,J(HH)=4.7Hz,1H,C6H),9.44(d,J(HH)=3.6Hz,1H,C3H),9.37-9.33(m,2H,C5H and C11H),8.98(d,J(HH)=11.4Hz,1H,C8H),6.94(m,C9H),6.53(m,1H,C10H),1.51(s,3H),0.25(s,9H,TMS)and 7.79-5.66(69H,other aromatic protons).

[0241] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:10.54(s,CPPh3),and-21.25(s,OsPPh3).

[0242] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:222.1(d,J(PC)=24.3Hz,C4),210.4(t,J(PC)=14.4Hz,C7),187.8(s,C13),180.2(d,J(PC)=23.4Hz,C3),177.6(t,J(PC)=5.1Hz,C6),176.0(t,J(PC)=10.8Hz,C12),166.3(dt,J(PC)=10.5Hz,J(PC)=5.1Hz,C1),165.6(s,C15),165.2-164.2(BPh4,αC),150.4(s,C5),147.7(s,C8),142.2(s,C14),140.8(s,C11),129.7(s,C9),125.3(s,C10),122.9(dt,J(PC)=77.4Hz,J(PC)=3.5Hz,C2),21.9(s,CH3),4.4(s,TMS)and 154.1-114.4(other aromatic carbon atoms).

[0243] HRMS(ESI):(m / z)calcd for 1a[C 79 H68 O2OsP3SSi] + 1393.3532, found 1393.3528.

[0244] Example 2: Synthesis of

[55753] Osmium

[15] annulene 1b

[0245]

[0246] The complex P4b was synthesized according to existing literature (Nat. Commun. 2024, 14, 4378.). In an argon atmosphere, P4b (200 mg, 0.13 mmol) and p-toluenesulfonylacetylene (91 mg, 0.52 mmol) were dissolved in 1,2-dichloroethane (5 mL) and reacted at 55°C for 12 hours. After the solution was vacuum-evacuated, the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation (eluent: dichloromethane) to obtain a red solid compound 1b (127 mg, yield 57%). The structure of compound 1b was obtained by nuclear magnetic resonance. 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0247] 1 H NMR(600MHz,CDCl3,ppm)δ:9.78(d,J(HH)=1.5Hz,1H,C3H),9.27(s,1H,C8H),9.19(d,J(HH)=12.1Hz,1H,C 11H),9.15(d,J(HH)=3.6Hz,1H,C5H),8.97(d,J(HH)=3.6Hz,1H,C6H),6.99(br,C10H),2.24(s,3H,CH3)and 7.62-5.93(79H, other aromaticprotons).

[0248] 31 P{ 1 H}NMR(243MHz,CD2Cl2,ppm)δ:11.05(s,CPPh3),-17.03(s,OsPPh3).

[0249] 13 C{ 1 H}NMR (151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13C HSQC and 1 H- 13 C HMBC, ppm) δ: 218.1 (t, J = 13.3Hz, C7), 216.9 (d, J (PC) = 23.4Hz, C4), 177.5 (t, J (PC) = 9.5Hz, C1 2),176.7(s,C6),172.7(s,C13),171.1(d,J(PC)=21.8Hz,C3),165.8(dt,J(PC)=10.8Hz,J(PC )=5.2Hz,,C1),164.8-163.8(BPh4,αC),154.4(s,C15),150.9(s,C5),148.6(s,C8),143.5(s, C14),140.4(s,C11),126.6(s,C10),122.4(dt,J(PC)=8.8,J(PC)=3.9Hz,C2),21.4(s,CH3)and 148.5-119.1(other aromatic carbon atoms).

[0250] HRMS(ESI):(m / z)calcd for 1b[C 88 H 68 O2OsP3S] + 1473.3763, found 1473.3716.

[0251] Example 3: Synthesis of

[55753] Osmium

[15] annulene 1c

[0252]

[0253] Step 1) Synthesis of compound P3c

[0254] The complex P2c was synthesized according to existing literature (Nat. Commun. 2024, 14, 4378.). In an argon atmosphere, P2c (200 mg, 0.14 mmol) was dissolved in dichloromethane (5 mL), and then p-toluenesulfonyl chloride (200 mg, 0.14 mmol) was added. After the solution was reacted at room temperature for 12 hours, it was filtered with diatomaceous earth, and the filtrate was vacuum concentrated to about 2 ml, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as an eluent to obtain a green solid compound P3c (144 mg, yield 65%). The structure of compound P3c was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0255] 1 H NMR (600MHz, CD2Cl2, ppm) δ: 7.46 (d, J (HH) = 4.1Hz, 1H, C5H), 7.30 (d, J (HH) = 4.1Hz, 1H, C6H), 7. 22(br,1H,C8H),6.94(br,1H,C3H),5.57(s,1H,C10H),2.30(s,3H,C13H),1.69(s,3H,C12H),and 7.71-6.77(69H, other aromatic protons).

[0256] 31 P{ 1 H}NMR (243MHz, CD2Cl2, ppm) δ: 5.80 (t, J (PP) = 7.9 Hz, CPPh3), -3.65 (d, J (PP) = 7.9 Hz, OsPPh3).

[0257] 13 C{ 1 H}NMR (151MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:323.3(td,J(PC)=16.4,J(PC)=11.2Hz,C1),226.2(t,J(PC)=11.1Hz,C 7),200.3(t,J(PC)=12.1Hz,C11),188.1(d,J(PC)=30.0Hz,C4),164.6-163.6(BPh4 ,αC),159.6(s,C5),159.7(s,C6),151.4(t,J(PC)=3.1Hz,C9),142.3(m,C3),137.3 (s,C10),135.7(s,C8),121.4(d,J(PC)=90.6Hz,C2),26.1(s,C12),21.3(s,C13)and 143.2-121.4(otheraromatic carbon atoms).

[0258] HRMS(ESI):(m / z)calcd for P3c[C 73 H 60 O2OsP3S]+ 1285.3137, found 1285.3129.

[0259] Step 2) Synthesis of compound P4c

[0260] In an argon atmosphere, P3c (200 mg, 0.12 mmol) and phenylethynyl lithium (1.0 M in THF, 300 μL, 0.30 mmol) were dissolved in tetrahydrofuran (5 mL) and reacted at -10 ° C for 10 minutes. Then, saturated NH4Cl aqueous solution (2 mL) was added to the solution, and the organic phase was extracted with dichloromethane. After vacuum drying, the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation (eluent: dichloromethane) to obtain a red solid compound P4c (145 mg, yield 75%). The structure of compound P4c was obtained by nuclear magnetic resonance. 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0261] 1 H NMR (600MHz, CDCl3, ppm) δ: 7.96 (d, J (PH) = 3.0Hz, 1H, C5H), 7.59 (s, 1H, C6H), 7.55(s,1H,C3H),6.07(s,1H,C8H),4.56(s,1H,C10H),1.72(s,3H,C14H),and 7.58-6.65(70H, other aromatic protons).

[0262] 31 P{ 1 H}NMR (243MHz, CDCl3, ppm) δ: 8.34 (t, J (PP) = 5.8 Hz, CPPh3), and -4.36 (d, J (PP) = 5.8 Hz, OsPPh3).

[0263] 13 C{ 1 H}NMR (151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13C HMBC,ppm)δ:330.0(t,J(PC)=15.3Hz,C11),220.9(m,C7),203.8(m,C4),187.6(td, J(PC)=13.0, J(PC)=7.8Hz,C1),165.1-164.2(BPh4,αC),164.8(s,C9),157.8(s,C5) ,157.5(s,C6),137.8(m,C12),135.6(d,J(PC)=24.9Hz,C3),127.3(s,C8),121.2(d ,J(PC)=85.8Hz,C2),118.3(s,C10),104.6(d,J(PC)=12.6Hz,C13),23.8(s,C14)and 136.7-115.8(otheraromatic carbon atoms).

[0264] HRMS(ESI):(m / z)calcd for P4c[C 74 H 58 OsP3] + 1231.3361, found 1231.3344.

[0265] Step 3) Synthesis of

[55753] Osmium

[15] annulene 1c

[0266] In an argon atmosphere, P4c (200 mg, 0.13 mmol) and p-toluenesulfonylacetylene (91 mg, 0.52 mmol) were dissolved in 1,2-dichloroethane (5 mL) and reacted at 55°C for 12 hours. After the solution was vacuum-evacuated, the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation (eluent: dichloromethane) to obtain a red solid compound 1c (112 mg, yield 50%). The structure of compound 1c was confirmed by X-ray single crystal diffraction. Figure 1 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0267] 1H NMR(400MHz,CD2Cl2)δ:9.65(s,1H,C3H),9.16(d,J(HH)=3.8Hz,1H,C5H),8.94(m,2H,C6H and C11H),8.91(s,1H,C8H),6.56(d,J(HH)=12.1Hz,1H,C10H),2.31(s,3H,C17H),2.03(s,3H,C16H),and 7.69-5.94(74H,other aromatic protons).

[0268] 31 P{ 1 H}NMR(162MHz,CD2Cl2)δ:10.67(t,J(PP)=5.2Hz,CPPh3),-17.09(d,J(PP)=5.2Hz,OsPPh3).

[0269] 13 C{ 1 H}NMR(101MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:221.0(t,J(PC)=13.2Hz,C7),216.4(d,J(PC)=24.3Hz,C4),178.2(t,J(PC)=9.6Hz,C12),175.8(s,C6),172.1(s,C15),171.1(d,J(PC)=21.2Hz,C3),165.5(dt,J(PC)=9.8Hz,J(PC)=4.5Hz,C1),164.9-163.9(BPh4,αC),151.8(s,C5),149.2(s,C8),142.0(s,C13),141.8(s,C9),141.3(s,C14),139.2(s,C11),128.5(s,C10),119.6(d,J(PC)=89.2Hz,C2),31.9(s,C16),21.3(s,C17)and 154.6-121.8(other aromatic carbonatoms).

[0270] HRMS(ESI):(m / z)calcd for 1c[C 83 H 66 O2OsP3S] +1411.3606, found 1411.3617.

[0271] Example 4: Synthesis of

[55753] Osmium

[15] annulene 1d

[0272]

[0273] In an argon atmosphere, 1a (150 mg, 0.088 mmol) was dissolved in 1,2-dichloroethane (5 mL), and then KOH (123 mg, 2.2 mmol) and methanol (0.5 mL) were added. After the solution was reacted at room temperature for 2 hours, it was vacuum-evacuated, and the residue was dissolved in dichloromethane (10 mL), filtered, and the filtrate was concentrated to about 2 mL, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as an eluent to obtain a brown solid compound 1d (49.6 mg, yield 50%). The structure of compound 1d was confirmed by X-ray single crystal diffraction. Figure 2 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0274] 1 H NMR (600MHz, CDCl3, ppm) δ: 10.02 (d, J (HH) = 2.6 Hz, 1H, C3H), 10.00 (d, J (HH) = 11.3 Hz, 1H, C11H), 9.87 (d, J (HH) = 2.6 Hz, 1H, C2H), 9.46(d,J(HH)=10.8Hz,1H,C8H),9.39(d,J(HH)=3.8Hz,1H,C6H),9.14(d,J(HH)=3.8Hz,1H,C5H),7.79(d,J(HH)=8.2Hz,2H,Ar-H of Ts),7.66(t,J(HH)=10.8Hz,1H,C9H),7.39(t,J(HH)=11.3Hz,1H,C10H),6.99(t,J(HH)=7.4Hz,6H,H p of PPh3),6.95(d,J(HH)=8.2Hz,2H,Ar-H of Ts),6.75(t,J(HH)=7.4Hz,12H,H m of PPh3),5.51(dd,J(PH)=11.3Hz,J(HH)=4.9Hz,12H,H oof PPh3),2.28(s,3H,CH3),0.67(s,9H,TMS).

[0275] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-16.31(s,OsPPh3).

[0276] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:225.9(s,C4),201.6(t,J(PC)=12.9Hz,C7),183.6(s,C13),180.2(t,J(PC)=5.7Hz,C6),174.4(t,J(PC)=10.3Hz,C12),167.6(s,C3),166.5(t,J(PC)=4.4Hz,C1),161.8(s,C15),146.0(s,C8),145.2(s,C5),144.1(s,Ar-C of Ts),142.9(m,C2),141.8(s,Ar-C of Ts),139.6(s,C11),135.5(s,C14),133.9(t,J(PC)=5.0Hz,C o of PPh3),130.4(t,J(PC)=23.9Hz,CP of PPh3),129.1(s,Ar-Cof Ts),128.8(s,Ar-C of Ts),127.8(s,C p of PPh3),126.7(s,C9),126.0(t,J(PC)=4.4Hz,C m of PPh3),122.5(s,C10),21.7(s,CH3),2.6(s,TMS).

[0277] HRMS(ESI):(m / z)[M+H] + calcd for 1d[C 61 H 55 O2OsP2SSi] + 1133.2777,found1133.2740.

[0278] Example 5: Synthesis of

[55753] Osmium

[15] annulene 1e

[0279]

[0280] In an argon atmosphere, 1b (150 mg, 0.084 mmol) was dissolved in 1,2-dichloroethane (5 mL), and then KOH (117 mg, 2.1 mmol) and methanol (0.5 mL) were added. After the solution was reacted at room temperature for 2 hours, it was vacuum-evacuated, and the residue was dissolved in dichloromethane (10 mL), filtered, and the filtrate was vacuum-evacuated. Then, ether (15 mL) and CaBr2 (334 mg, 1.67 mmol) were added and reacted at room temperature for 3 hours. The solution was filtered and the filtrate was concentrated to obtain a brown solid compound 1e (78 mg, yield 77%). The structure of compound 1e was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0281] 1 H NMR (600MHz, CDCl3, ppm) δ: 9.94 (s, 1H, C3H), 9.79 (d, J (HH) = 12.0Hz, 1H, C11H), 9.57 (s, 1H, C8 H),9.38(s,1H,C2H),9.27(d,J(HH)=2.5Hz,1H,C6H),9.16(d,J(HH)=2.2Hz,1H,C5H),7.82(d,J (HH)=7.3Hz,2H,Ar-H),7.55(t,J(HH)=7.3Hz,3H,Ar-H),7.50(m,1H,C10H),7.28(m,3H,Ar-H) ,7.21(d,J(HH)=7.1Hz,2H,Ar-H),7.11(d,J(HH)=7.8Hz,2H,Ar-H),7.03(t,J(HH)=7.2Hz,6H,H p of PPh3),6.82(t,J(HH)=7.4Hz,12H,H m of PPh3),6.75(d,J(HH)=7.9Hz,2H,Ar-H),5.74(dd,J(PH)=11.3Hz,J(HH)=5.9Hz,12H,H o of PPh3),2.26(s,3H,CH3).

[0282] 31 P{1 H}NMR(243MHz,CDCl3,ppm)δ:-14.32(s,OsPPh3).

[0283] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:223.5(s,C4),204.5(t,J(PC)=12.6Hz,C7),178.0(t,J(PC)=5.6Hz,C6),172.5(t,J(PC)=9.7Hz,C12),170.1(s,C13),165.9(s,C3),162.8(t,J(PC)=4.3Hz,C1),151.5(s,C15),150.8(s,C9),146.8(s,C8),145.9(s,C5),144.0(s,Ar-C),142.2(s,Ar-C),141.5(s,Ar-C),141.4(t,J(PC)=4.5Hz,C2),138.9(s,C13),138.3(s,C11),133.8(t,J(PC)=4.4Hz,C o of PPh3),130.0(t,J(PC)=24.0Hz,CP of PPh3),129.4(s,Ar-C),128.9(s,Ar-C),128.8(s,C p of PPh3),128.6(s,Ar-C),128.6(s,Ar-C),128.4(s,Ar-C),128.4(s,Ar-C),127.9(s,Ar-C),126.9(s,Ar-C),126.4(s,Ar-C),126.1(t,J(PC)=4.2Hz,C m of PPh3),124.5(s,C10),21.4(s,CH3).

[0284] HRMS(ESI):(m / z)[M+H] + calcd for 1e[C 70 H 55 O2OsP2S] + 1213.3008,found1213.3005.

[0285] Example 6: Synthesis of

[55753] Osmium

[15] annulene 1f

[0286]

[0287] In an argon atmosphere, 1c (150 mg, 0.084 mmol) was dissolved in 1,2-dichloroethane (5 mL), and then KOH (117 mg, 2.1 mmol) and methanol (0.5 mL) were added. After the solution was reacted at room temperature for 2 hours, it was vacuum-evacuated, and the residue was dissolved in dichloromethane (10 mL), filtered, and the filtrate was vacuum-evacuated. Then, ether (15 mL) and CaBr2 (334 mg, 1.67 mmol) were added and reacted at room temperature for 3 hours. The solution was filtered and the filtrate was concentrated to obtain a brown solid compound 1f (70.8 mg, yield 71%). The structure of compound 1f was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0288] 1 H NMR (600MHz, CDCl3, ppm) δ: 9.85 (d, J (HH) = 3.0 Hz, 1H, C3H), 9.49 (d, J (HH) = 12.0 Hz,1H,C11H),9.28(d,J(HH)=3.0Hz,1H,C2H),9.17(s,1H,C8H),9.08(br,2H,C5H andC6H),7.24(m,3H,Ar-H),7.17(d,J(HH)=7.0Hz,2H,Ar-H),7.11(d,J(HH)=8.2Hz,2H,Ar-H),7.04(t,J(HH)=7.4Hz,6H,H p of PPh3),7.02(br,1H,C10H),6.81(t,J(HH)=7.4Hz,12H,H m of PPh3),6.76(d,J(HH)=8.2Hz,2H,Ar-H),5.73(dd,J(PH)=12.0Hz,J(HH)=5.0Hz,12H,H o of PPh3),2.44(s,3H,C16H),2.26(s,3H,C17H).

[0289] 31 P{ 11H NMR (162 MHz, CDCl3, ppm) δ: -14.13 (s, OsPPh3).

[0290] 13 C{ 1 1H NMR (151 MHz, CDCl3, plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC, ppm) δ: 221.9 (s, C4), 207.8 (t, J(PC) = 12.0 Hz, C7), 176.1 (t, J(PC) = 5.4 Hz, C6), 173.9 (t, J(PC) = 9.4 Hz, C12), 168.5 (s, C13), 165.1 (d, J(PC) = 2.9 Hz, C3), 162.1 (t, J(PC) = 4.9 Hz, C1), 151.7 (s, C15), 146.9 (s, C8), 146.4 (s, C5), 144.1 (s, C14), 142.4 (s, Ar-C), 141.4 (s, Ar-C), 140.7 (t, J(PC) = 4.2 Hz, C2), 137.5 (s, C11), 135.6 (s, C9), 133.9 (t, J(PC) = 4.4 Hz, C o of PPh3), 132.7 (s, Ar-C), 130.2 (t, J(PC) = 23.9 Hz, CP of PPh3), 129.5 (s, Ar-C), 128.8 (s, C p of PPh3), 128.4 (s, Ar-C), 127.9 (s, Ar-C), 126.9 (s, Ar-C), 126.0 (t, J(PC) = 4.4 Hz, C m of PPh3), 125.9 (br, C10), 32.1 (s, C16), 21.5 (s, C17).

[0291] HRMS (ESI): (m / z) calcd for 1f [C 65 H 52 O2OsP2S] + 1150.2778, found 1150.2775.

[0292] Example 7:

[55735] Osmium

[15] annulene 2a

[0293]

[0294] In an air atmosphere, 1d (61 mg, 0.054 mmol) was dissolved in dichloromethane (5 mL), and then AlCl3 (72 mg, 0.54 mmol) and Al2O3 (1.0 g) were added. After the solution was reacted at room temperature for 12 hours, it was concentrated in vacuo to about 2 mL, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as the eluent to obtain a yellow solid compound 2a (35 mg, yield 64%). The structure of compound 2a was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0295] 1 H NMR (600MHz, CDCl3, ppm) δ: 9.92 (d, J (HH) = 10.3Hz, 1H, C8H), 9.46 (d, J (HH) = 3.2Hz, 1H, C2H), 9.43 (d, J (HH) = 8.4Hz, 1H, C11H), 9.33 (d, J (HH) = 3.2Hz, 1H ,C3H),8.74(d,J(HH)=4.0Hz,1H,C6H),8.36(d,J(HH)=4.0Hz,1H,C5H),8.3 0(m,1H,C10H),7.90(t,J(HH)=10.3Hz,1H,C9H),7.00(t,J(HH)=7.5Hz,6H,H p of PPh3),6.80(t,J(HH)=7.5Hz,12H,H m of PPh3),5.60(m,12H,H o of PPh3),0.42(s,9H,TMS).

[0296] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-15.15(s,OsPPh3).

[0297] 13 C{ 1 H}NMR (151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13C HMBC,ppm)δ:225.7(m,C4),185.8(m,C1),182.8(m,C7),175.5(s,C12),169.6(s,C6),160.3 (s,C13),153.3(s,C2),151.1(s,C3),145.9(s,C5),143.3(s,C8),137.2(s,C14),133.8(s,C o of PPh3),129.9(t,J(PC)=22.8Hz,CP of PPh3),128.4(s,C p of PPh3),128.9(s,C15),126.8(s,C9),125.8(s,C m of PPh3),122.9(s,C11),119.3(s,C10),-0.9(s,TMS).

[0298] HRMS(ESI):(m / z)calcd for 2a[C 54 H 47 ClOsP2Si] + 1012.2226, found 1012.2203.

[0299] Example 8: Synthesis of

[55735] Osmium

[15] annulene 2b

[0300]

[0301] In an air atmosphere, 1e (66 mg, 0.054 mmol) was dissolved in dichloromethane (5 mL), and then AlCl3 (72 mg, 0.54 mmol) and Al2O3 (1.0 g) were added. After the solution was reacted at room temperature for 12 hours, it was concentrated in vacuo to about 2 mL, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as an eluent to obtain a yellow solid compound 2b (46 mg, yield 77%). The structure of compound 2b was confirmed by X-ray single crystal diffraction. Figure 3 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0302] 1H NMR(400MHz,CDCl3,ppm)δ:10.31(s,1H,C8H),9.72(d,J(HH)=3.4Hz,1H,C2H),9.45(d,J(HH)=8.8Hz,1H,C11H),9.28(d,J(HH)=3.4Hz,1H,C3H),8.88(d,J(HH)=4.4Hz,1H,C6H),8.64(d,J(HH)=8.8Hz,1H,C10H),8.33(br,1H,C5H),8.00(d,J(HH)=7.5Hz,2H,Hof Ph),7.94(d,J(HH)=7.5Hz,2H,H of Ph),7.61(t,J(HH)=7.5Hz,2H,H of Ph),7.49(t,J(HH)=7.5Hz,1H,H of Ph),7.46(t,J(HH)=7.5Hz,2H,H of Ph),7.41(t,J(HH)=7.1Hz,1H,H of Ph),6.98(t,J(HH)=7.4Hz,6H,H p of PPh3),6.78(t,J(HH)=7.4Hz,12H,H m of PPh3),5.70(d,J(HH)=7.4Hz,12H,H o of PPh3).

[0303] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-14.86(s,OsPPh3).

[0304] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:227.0(m,C4),183.0(m,C7),181.5(m,C1),169.5(s,C6),161.6(s,C15),155.5(s,C13),153.3(m,C12),153.1(s,C2),151.0(s,C3),146.7(s,C8),146.3(s,C5),140.5(s,C14),140.2(s,C9),134.9(s,C of Ph),133.5(s,C oof PPh3),129.7(s,C of Ph),129.5(m,CP of PPh3),129.2(s,C of Ph),128.5(s,C p of PPh3),128.2(s,C of Ph),128.1(s,C of Ph),126.6(s,C of Ph),125.9(s,C m of PPh3),125.6(s,C of Ph),121.8(s,C10),119.2(s,C11),107.9(s,C of Ph).

[0305] HRMS(ESI):(m / z)calcd for 2b[C 63 H 47 ClOsP2] + 1092.2456, found 1092.2450.

[0306] Example 9: Synthesis of

[55735] Osmium

[15] annulene 2c

[0307]

[0308] In an air atmosphere, 1f (62 mg, 0.054 mmol) was dissolved in dichloromethane (5 mL), and then AlCl3 (72 mg, 0.54 mmol) and Al2O3 (1.0 g) were added. After the solution was reacted at room temperature for 12 hours, it was concentrated in vacuo to about 2 mL, and then loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as the eluent to obtain a yellow solid compound 2c (41 mg, yield 74%). The structure of compound 2c was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0309] 1H NMR(600MHz,CDCl3,ppm)δ:9.96(s,1H,C8H),9.69(d,J(HH)=2.8Hz,1H,C2H),9.33(d,J(HH)=8.9Hz,1H,C11H),9.25(d,J(HH)=2.8Hz,1H,C3H),8.78(d,J(HH)=4.1Hz,1H,C6H),8.37(m,2H,C10H and C5H),7.99(d,J(HH)=7.2Hz,2H,H of Ph),7.46(t,J(HH)=7.2Hz,2H,H of Ph),7.41(d,J(HH)=7.2Hz,1H,H of Ph),6.98(t,J(HH)=7.4Hz,6H,H p of PPh3),6.78(t,J(HH)=7.4Hz,12H,H m of PPh3),5.67(dd,J(PH)=11.5Hz,J(HH)=4.6Hz,12H,H o of PPh3),3.01(s,3H,CH3).

[0310] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-15.08(s,OsPPh3).

[0311] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:226.5(t,J(PC)=6.2Hz,C4),184.1(t,J(PC)=9.4Hz,C7),180.5(t,J(PC)=6.2Hz,C1),168.9(s,C6),160.5(s,C15),155.0(s,C13),152.8(s,C2),150.6(s,C3),147.3(s,C8),145.9(s,C5),140.5(s,C14),134.9(s,C9),134.7(C12),133.5(t,J(PC)=5.0Hz,C oof PPh3),129.7(t,J(PC)=23.1Hz,CP of PPh3),129.3(s,C of Ph),128.4(s,C p ofPPh3),128.0(s,C of Ph),126.5(s,C of Ph),125.8(t,J(PC)=4.5Hz,C m of PPh3),121.0(s,C10),118.6(s,C11),106.1(s,C of Ph),33.4(s,CH3).

[0312] HRMS(ESI):(m / z)calcd for 2c[C 58 H 45 ClOsP2] + 1030.2300, found 1030.2279.

[0313] Example 10: Synthesis of

[55663] Osmium

[15] annulene 3a

[0314]

[0315] In an argon atmosphere, 1d (61 mg, 0.054 mmol) was dissolved in THF (5 mL). The solution was reacted at 80°C for 96 hours and then vacuum-dried. The residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as the eluent to obtain a brown solid compound 3a (7.5 mg, yield 15%). The structure of compound 3a was confirmed by X-ray single crystal diffraction. Figure 4 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0316] 1H NMR(600MHz,CDCl3,ppm)δ:10.20(d,J(HH)=2.5Hz,1H,C2H),10.13(s,1H,C3H),9.64(d,J(HH)=3.7Hz,1H,C6H),9.49(d,J(HH)=3.3Hz,1H,C5H),8.93(s,1H,C12H),8.46(m,2H,C10H and C9H),8.40(d,J(HH)=7.0Hz,1H,C8H),2.32(s,3H,CH3),0.66(s,9H,TMS),and 7.73-5.33(34H,other aromatic protons).

[0317] 31 P{ 1 H}NMR(162MHz,CDCl3,ppm)δ:-24.39(s,OsPPh3).

[0318] 13 C{ 1 H}NMR(151MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC,ppm)δ:219.1(d,J(PC)=2.9Hz,C4),208.9(t,J(PC)=11.2Hz,C7),181.2(t,J(PC)=11.3Hz,C11),172.4(t,J(PC)=5.2Hz,C6),168.8(t,J(PC)=3.0Hz,C1),160.5(s,C3),157.7(t,J(PC)=5.1Hz,C10),151.7(s,C5),146.3(s,C15),144.9(s,C2),141.6(s,C13),141.1(d,J(PC)=3.3Hz,C8),139.7(s,C12),131.5(s,C9),115.6(s,C14),21.6(s,CH3),3.8(s,TMS),and 142.2-125.7(other aromatic carbon atoms).

[0319] HRMS(ESI):(m / z)calcd for 3a[C 61 H 54 O2OsP2SSi] +1132.2704, found 1132.2720.

[0320] Example 11: Synthesis of

[55636] Osmium

[15] annulene 4a

[0321]

[0322] In an argon atmosphere, 1d (50.0 mg, 0.044 mmol) and 1-chloro-1,3-dihydro-3,3-dimethyl-1,2-benzimidoxolan (19.6 mg, 0.066 mmol) were dissolved in 1,2-dichloroethane (5 mL). After reacting at room temperature for 12 hours, the solution was vacuum-evacuated and the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation. Using dichloromethane as the eluent, a brown solid compound 4a (14.1 mg, yield 29%) was obtained. The structure of compound 4a was confirmed by X-ray single crystal diffraction. Figure 5 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0323] 1 H NMR(600MHz,CDCl3,ppm)δ:The protons of C2H,C3H,C5H,C6H,C8H,C9H,C10Hand C14H(totally 8H)resonant at 9.74(m,2H),9.40(d,J(HH)=3.1Hz,1H),9.32(d,J(HH)=4.4Hz,2H),8.92(s,1H),8.77(t,J(HH)=7.5Hz,1H),and 8.42(d,J(HH)=8.3Hz,1H); 7.84(d,J(HH)=8.2Hz,2H,Ar-H of Ts),7.00(t,J(HH)=7.1Hz,6H,H p ofPPh3),6.97(d,J(HH)=8.2Hz,2H,Ar-H of Ts),6.75(t,J(HH)=7.4Hz,12H,H m of PPh3),5.33(dd,J(PH)=11.3Hz,J(HH)=4.9Hz,12H,H o of PPh3),2.23(s,3H,CH3).

[0324] 31 P{ 1 H} NMR (243 MHz, CDCl3, ppm) δ: -34.70 (s, OsPPh3).

[0325] 13 C{ 1 H} NMR (151 MHz, CDCl3, plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC, ppm) δ: The carbon atoms of annulene (totally 15C) resonant at 222.9 (s), 194.63 (t, J(PC) = 11.9 Hz), 183.10 (t, J(PC) = 12.0 Hz), 174.85 (t, J(PC) = 7.9 Hz), 168.65 (t, J(PC) = 7.6 Hz), 147.90 (t, J(PC) = 4.3 Hz), 147.13 (t, J(PC) = 4.1 Hz), 146.04 (t, J(PC) = 5.2 Hz), 142.92 (t, J(PC) = 5.2 Hz), 140.0 (m, 2C), 132.9 (t, J(PC) = 4.4 Hz), 132.7 (s), 126.8 (s), 126.7 (s); 142.40 (s, Ar-C of Ts), 141.0 (s, Ar-C of Ts), 133.1 (t, J(PC) = 4.3 Hz, C o of PPh3), 129.5 (s, Ar-C of Ts), 128.0 (t, J(PC) = 24.0 Hz, CP of PPh3), 128.8 (s, C p of PPh3), 127.7 (s, Ar-C of Ts), 125.8 (t, J(PC) = 4.3 Hz, C m of PPh3).

[0326] HRMS (ESI): (m / z) calcd for 4a [C 58 H 45 ClO2OsP2S] + 1094.1919, found 1094.1907.

[0327] Example 12: Synthesis of Osmabenzene

[15] Annulene 5a

[0328]

[0329] 2a (50.0 mg, 0.049 mmol) was dissolved in dichloromethane (5 mL) at room temperature in an argon atmosphere. HCl·H2O (4M, 49 μL, 1.96 mmol) was injected into the solution. After reacting at room temperature for 12 hours, the solvent was evacuated under vacuum until about 2 mL remained. The residue was loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as an eluent to obtain a yellow solid compound 5a (32.5 mg, yield 70%). The structure of compound 5a was confirmed by X-ray single crystal diffraction. Figure 6 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0330] 1 H NMR(600MHz,CD2Cl2,ppm)δ:The protons of C2H,C3H,C5H,C6H,C8H,C9H,C11H,C12H and C14H(totally 9H)resonant at 9.46(s,1H),9.44(m,3H),9.40(s,1H),9.36(m,2H),9.21(s,1H),and 9.19(s,1H); 6.79(t,J(HH)=7.3Hz,6H,H p of PPh3),6.75(t,J(HH)=7.3Hz,12H,H m of PPh3),5.41(dd,J(PH)=12.3Hz,J(HH)=5.1Hz,12H,H o ofPPh3).

[0331] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-17.65(s,OsPPh3).

[0332] 13 C{ 1H}NMR(151MHz,CD2Cl2,ppm)δ:The carbon atoms of C1,C4,C7,C10 and C13(totally 5C)resonant at The carbon atoms of C2,C3,C5,C6,C8,C9,C11,C12 and C14(totally 9C)resonant at 151.8(s),151.4(s),151.4(s),151.2(s),151.1(s),151.0(s),149.6(s),148.3(s),146.5(s);140.9(s,C15),133.7(t,J(PC)=5.0Hz,C o of PPh3),131.5(t,J(PC)=23.9Hz,CP of PPh3),128.8(s,C p of PPh3),125.7(t,J(PC)=5.1Hz,C m of PPh3).

[0333] HRMS(ESI):(m / z)calcd for 5a[C 51 H 39 ClOsP2] + 940.1830, found 940.1832.

[0334] Example 13: Synthesis of

[55555] Osmium

[15] annulene 5b

[0335]

[0336] At room temperature, in an argon atmosphere, 2b (50.0 mg, 0.046 mmol) was dissolved in dichloromethane (5 mL). HCl·H2O (4M, 45 μL, 1.83 mmol) was injected into the solution. After reacting at room temperature for 12 hours, the solvent was evacuated under vacuum until about 2 mL remained. The residue was loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as the eluent to obtain a yellow solid compound 5b (32.2 mg, yield 64%). The structure of compound 5b was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0337] 1 H NMR (400MHz, CDCl3, ppm) δ: 9.68 (d, J (HH) = 3.6 Hz, 1H, C2H), 9.62 (s, 1H, C8H), 9.45 (d, J (HH) = 3. 8Hz,1H,C11H),9.35(d,J(HH)=3.4Hz,1H,C6H),9.28(d,J(HH)=3.8Hz,1H,C12H),9.19(m,2H,C3H and C5H),7.57-7.48(m,8H,H of Ph),7.12-7.10(m,2H,H ofPh),6.98(t,J(HH)=7.5Hz,6H,H p of PPh3),6.77(t,J(HH)=7.5Hz,12H,H m of PPh3),5.55(m,12H,H o of PPh3).

[0338] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-18.39(s,OsPPh3).

[0339] 13 C{ 1 H}NMR (101MHz,CDCl3,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13C HMBC,ppm)δ:200.3(t,J(PC)=7.0Hz,C4),196.1(t,J(PC)=6.9Hz,C7),192.7(t,J(PC)=7.2Hz,C10),186.5(t,J(PC) )=7.1Hz,C13),183.0(t,J(PC)=7.4Hz,C1),162.0(s,C9),157.2(s,C14),153.3(s,C8),152.4(s,C6),150.8(s)and 150.4(s)(C3 and C5),149.5(s,C12),149.3(s,C11),147.3(s,C2),141.5(s,C of Ph),141.0(s,C15),140.8(s,C of Ph),133.3(t,J(PC)=4.6Hz,C o of PPh3),131.8(s,C of Ph),131.6(s,C of Ph),130.8(t,J(PC)=24.6Hz,CP of PPh3),128.5(s,C p of PPh3),127.9(s,C of Ph),127.2(s,C of Ph),126.7(s,C of Ph),126.3(s,C of Ph),125.7(t,J(PC)=4.6Hz,C m of PPh3).

[0340] HRMS(ESI):(m / z)calcd for 5b[C 63 H 47 ClOsP2] + 1092.2456, found 1092.2438.

[0341] Example 14: Synthesis of

[55555] Osmium

[15] annulene 5c

[0342]

[0343] 2c (50.0 mg, 0.048 mmol) was dissolved in dichloromethane (5 mL) at room temperature in an argon atmosphere. HCl·H2O (4M, 48 μL, 1.92 mmol) was injected into the solution. After reacting at room temperature for 12 hours, the solvent was evacuated under vacuum until about 2 mL remained. The residue was loaded into a 200-300 mesh silica gel column for column chromatography separation. Dichloromethane was used as the eluent to obtain a yellow solid compound 5c (30.6 mg, yield 61%). The structure of compound 5c was obtained by nuclear magnetic resonance 1 H.31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0344] 1 H NMR(600MHz,CD2Cl2,ppm)δ:The protons of C2H,C3H,C5H,C6H,C8H,C11H andC12H(totally 7H)resonant at 9.68(d,J(HH)=3.2Hz,1H),9.29(d,J(HH)=2.7Hz,1H),9.28(d,J(HH)=3.1Hz,1H),9.26(d,J(HH) =3.5Hz,1H),9.24(d,J(HH)=2.7Hz,1H),9.18(s,1H),and9.08(d,J(HH)=3.4Hz,1H);7.49(m,3H,H of Ph),7.09(d,J(HH)=7.3Hz,2H,Hof Ph),6.99(t,J(HH)=7.4Hz,6H,H p of PPh3),6.78(t,J(HH)=7.4Hz,12H,H m of PPh3),5.50(dd,J(PH)=12.2Hz,J(HH)=5.2Hz,12H,H o of PPh3),2.88(s,3H,CH3).

[0345] 31 P{ 1 H}NMR(243MHz,CD2Cl2,ppm)δ:-17.72(s,OsPPh3).

[0346] 13 C{ 11H NMR (151 MHz, CD2Cl2, ppm) δ: The carbon atoms of C1, C4, C7, C10 and C13 (totally 5 C) resonate at 199.2 (t, J(PC) = 7.1 Hz), 196.7 (t, J(PC) = 7.3 Hz), 195.2 (t, J(PC) = 7.2 Hz), 185.3 (t, J(PC) = 7.1 Hz), and 182.4 (t, J(PC) = 7.2 Hz); The carbon atoms of C2, C3, C5, C6, C8, C11 and C12 (totally 7 C) resonate at 154.1 (s), 151.0 (s), 150.5 (s), 150.4 (s), 147.8 (s), 146.4 (s), 146.1 (s); 158.5 (s, C9), 156.8 (s, C14), 140.8 (s, C of Ph), 140.2 (s, C15), 133.1 (t, J(PC) = 4.5 Hz, C o of PPh3), 131.6 (s, C of Ph), 131.0 (t, J(PC) = 24.9 Hz, CP of PPh3), 128.3 (s, C p of PPh3), 127.1 (s, C of Ph), 126.6 (s, C of Ph), 125.4 (t, J(PC) = 4.4 Hz, C m of PPh3), 17.2 (s, CH3).

[0347] HRMS (ESI): (m / z) calcd for 5c[C 58 H 45 ClOsP2] + 1030.2300, found 1030.2294.

[0348] Example 15: Synthesis of Osmium

[15] annulene 5d

[0349]

[0350] 5a (20.0 mg, 0.021 mmol) was dissolved in THF (5 mL) at room temperature in an argon atmosphere. t-BuLi (1.3 M, 0.13 mmol, 1.0 mL) was added dropwise to the solution at -40°C. After the reaction was maintained at the temperature for 20 minutes, methanol (2 mL) was added to the solution. The solvent was drained under vacuum and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as the eluent to obtain a yellow solid compound 5d (15.4 mg, yield 80%). The structure of compound 5d was confirmed by X-ray single crystal diffraction. Figure 7 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0351] 1 H NMR(850MHz,1,1,2,2-tetrachloroethane-d2,ppm)δ:9.43(s,10H,CH ofannulene),6.99(t,J(HH)=7.0Hz,6H,H p of PPh3),6.76(t,J(HH)=7.0Hz,12H,H m ofPPh3),5.51(dd,J(PH)=12.0Hz,J(HH)=5.0Hz,12H,H o of PPh3).

[0352] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-17.18(s,OsPPh3).

[0353] 13 C{ 1 H}NMR(151MHz,1,1,2,2-tetrachloroethane-d2,ppm)δ:198.1(m,OsC),150.0(s,CH of annulene),133.7(t,J(PC)=4.3Hz,C o of PPh3),131.5(t,J(PC)=23.9Hz,CP of PPh3),127.9(s,C p of PPh3),124.9(t,J(PC)=4.6Hz,C mof PPh3).

[0354] HRMS(ESI):(m / z)calcd for 5d[C 51 H 40 OsP2] + 906.2220, found 906.2216.

[0355] Example 16: Synthesis of

[55555] Osmium

[15] annulene 5e

[0356]

[0357] 5b (20.0 mg, 0.021 mmol) was dissolved in THF (5 mL) at room temperature in an argon atmosphere. t-BuLi (1.3 M, 0.13 mmol, 1.0 mL) was added dropwise to the solution at -40°C. After the reaction was maintained at the temperature for 20 minutes, methanol (2 mL) was added to the solution. The solvent was drained under vacuum and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as the eluent to obtain a yellow solid compound 5e (16.0 mg, yield 72%). The structure of compound 5e was obtained by nuclear magnetic resonance. 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0358] 1 H NMR (600MHz, CD2Cl2, ppm) δ: 9.60 (br, 2H, C8H and C15H), 9.50 (br, 2H, C11H and C12H), 9.33 (d, J (HH) = 3.1Hz, 2H, C2H and C6H), 9.27 (d, J (HH) = 3.1Hz, 2H, C3H andC5H),7.58(m,8H,H of Ph),7.09(m,2H,H of Ph),6.95(t,J(HH)=7.5Hz,6H,H p of PPh3),6.72(t,J(HH)=7.5Hz,12H,H m of PPh3),5.49(dd,J(PH)=11.9Hz,J(HH)=4.8Hz,12H,H o of PPh3).

[0359] 31 P{ 11H NMR (243 MHz, CDCl3, ppm) δ: -17.58 (s, OsPPh3).

[0360] 13 C{ 1 1H NMR (151 MHz, CDCl3, plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC, ppm) δ: 199.3 (t, J(PC) = 7.3 Hz, C4), 195.3 (t, J(PC) = 7.2 Hz, C1 and C7), 192.0 (t, J(PC) = 7.2 Hz, C10 and C13), 161.1 (s, C9 and C14), 152.9 (s, C8 and C15), 151.3 (s, C2 and C6), 150.3 (s, C3 and C5), 149.4 (s, C11 and C12), 141.6 (s, C of Ph), 133.3 (t, J(PC) = 4.5 Hz, C o of PPh3), 131.8 (s, C of Ph), 131.3 (t, J(PC) = 24.6 Hz, CP of PPh3), 128.3 (s, C of Ph), 127.9 (s, C p of PPh3), 126.2 (s, C of Ph), 125.4 (t, J(PC) = 4.5 Hz, C m of PPh3).

[0361] HRMS (ESI): (m / z) calcd for 5e[C 63 H 48 OsP2] + 1058.2846, found 1058.2874.

[0362] Example 17: Synthesis of Osmium

[15] annulene 5f

[55555]

[0363]

[0364] 5c (20.0 mg, 0.021 mmol) was dissolved in THF (5 mL) at room temperature in an argon atmosphere. t-BuLi (1.3 M, 0.13 mmol, 1.0 mL) was added dropwise to the solution at -40°C. After the reaction was maintained at the temperature for 20 minutes, methanol (2 mL) was added to the solution. The solvent was drained under vacuum and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as the eluent to obtain a yellow solid compound 5f (14.0 mg, yield 67%). The structure of compound 5f was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0365] 1 H NMR(600MHz,CD2Cl2,ppm)δ:9.63(s,1H,C15H),9.39(br,1H,C12H),9.37(br,2H,C11H and C6H),9.32(br,1H,C5H),9.30(br,1H,C2H),9.20(br,1H,C3H),9.11(s,1H,C8H),7.56(m,5H,H of Ph),7.47(d,J(HH)=6.4Hz,1H,H of Ph),6.94(t,J(HH)=7.4Hz,6H,H p of PPh3),6.72(t,J(HH)=7.4Hz,12H,H m of PPh3),5.46(dd,J(PH)=11.5Hz,J(HH)=4.9Hz,12H,H o of PPh3),2.94(s,3H,CH3).

[0366] 31 P{ 1 H}NMR(243MHz,CD2Cl2,ppm)δ:-16.89(s,OsPPh3).

[0367] 13 C{ 1 H}NMR (151MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13C HMBC, ppm) δ: 198.8 (t, J (PC) = 7.2Hz, C1), 196.4 (t, J (PC) = 7.1Hz, C7), 195.4 (t, J (PC) = 7.1Hz, C4), 194.6 (t, J (PC) = 7.4Hz, C10),191.5(t,J(PC)=7.3Hz,C13),161.4(s,C14),158.1(s,C9),154.2(s,C8),153.1(s,C15),150.7(s,C5),150.7(br,C2 and C6),149.7(s,C3),148.4(s,C12),147.2(s,C11),142.3(s,C of Ph),133.8(t,J(PC)=4.5Hz,C o of PPh3),132.3(s,C of Ph),132.1(t,J(PC)=23.5Hz,CP of PPh3),128.6(s,C p of PPh3),128.3(s,C of Ph),126.5(s,C of Ph),125.7(t,J(PC)=5.0Hz,C m of PPh3),17.7(s,CH3).

[0368] HRMS(ESI):(m / z)calcd for 5f[C 58 H 46 OsP2] + 996.2690, found 996.2690.

[0369] Example 18: Synthesis of 5 g of

[55555] Osmium

[15] annulene

[0370]

[0371] In an argon atmosphere, 5d (10.0 mg, 0.011 mmol) was dissolved in 1,2-dichlorobenzene (5 mL), and PEt3 (15 μL, 0.11 mmol) was added to the solution. After the system was sealed, the reaction was carried out at 180°C for 36 hours. After the solution cooled to room temperature, the solvent was drained under vacuum, and the residue was loaded into a 200-300 mesh silica gel column for column chromatography separation. Using n-hexane as the eluent, a yellow solid compound 5g (5.9 mg, yield 87%) was obtained. The structure of compound 5g was obtained by nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0372] 1 H NMR (400MHz, CDCl3, ppm) δ: 9.79 (s, 10H, CH of annulene), -0.56 (dt, J (PH) = 14.0Hz, J (HH) = 7.4Hz, 18H, CH3), -1.28 (m, 12H, CH2).

[0373] 31 P{ 1 H}NMR (243MHz, CDCl3, ppm) δ: -39.94 (s, OsPEt3).

[0374] 13 C{ 1 H}NMR (101MHz, CDCl3, ppm) δ: 197.4 (t, J (PC) = 7.4 Hz, OsC), 148.4 (s, CH ofannulene), 10.7 (t, J (PC) = 15.3 Hz, CH2), 7.4 (s, CH3).

[0375] HRMS(ESI):(m / z)calcd for 5g[C 27 H 40 OsP2] + 618.2220, found 618.2216.

[0376] Example 19: Synthesis of

[55555] Osmium

[15] annulene 5h

[0377]

[0378] In an argon atmosphere, 5d (10.0 mg, 0.011 mmol) was dissolved in dichloromethane (5 mL), and ICl (110 μL, 1 M, 0.11 mmol) was added to the solution. After reacting at room temperature for 12 hours, the solution was concentrated to about 2 mL, and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as an eluent to obtain a yellow solid compound 5h (9.4 mg, yield 83%). The structure of compound 5h was confirmed by X-ray single crystal diffraction. Figure 8 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0379] 1 H NMR(600MHz,CDCl3,ppm)δ:The protons of C2H,C3H,C5H,C6H,C8H,C9H,C11H,C12H and C15H(totally 9H)resonant at 9.46(m,2H),9.40-9.34(m,5H),9.21(d,J(HH)=3.1Hz,1H),and 9.11(d,J(HH)=3.5Hz,1H); 6.95(t,J(HH)=7.4Hz,6H,H p of PPh3),6.73(t,J(HH)=7.4Hz,12H,H m of PPh3),5.39(dd,J(PH)=12.2Hz,J(HH)=5.1Hz,12H,H o of PPh3).

[0380] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-17.18(s,OsPPh3).

[0381] 13 C{ 1 H}NMR(151MHz,CDCl3,ppm)δ:The carbon atoms of C1,C4,C7,C10 and C13(totally 5C)resonant at 199.9(m),199.8(m),198.3(t,J(PC)=7.2Hz),192.4(t,J(PC)=7.2Hz),and 188.2(t,J(PC)=7.1Hz);The carbon atoms of C2,C3,C5,C6,C8,C9,C11,C12,C14 and C15(totally 10C)resonant at 156.9(s),153.3(s),151.0(s),150.9(s),150.8(s),150.6(s),150.42(s),150.40(s),149.9(s),148.5(s); 133.3(t,J(PC)=4.5Hz,C o of PPh3),131.0(t,J(PC)=25.0Hz,CP of PPh3),128.2(s,Cp of PPh3),125.3(t,J(PC)=4.5Hz,C m of PPh3).

[0382] HRMS(ESI):(m / z)calcd for 5h[C 51 H 39 OsP2] + 1032.1186, found 1032.1210.

[0383] Example 20: Synthesis of

[55555] Osmium

[15] annulene 5i

[0384]

[0385] In an argon atmosphere, 5d (10.0 mg, 0.011 mmol) was dissolved in dichloromethane (5 mL), and t-BuONO (33 μL, 1 M, 0.033 mmol) was added to the solution. After reacting at room temperature for 12 hours, the solution was concentrated to about 2 mL, and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Using dichloromethane as an eluent, a red solid compound 5i (7.5 mg, yield 71%) was obtained. Under the same reaction conditions, replacing t-BuONO with NO2BF4 (0.033 mmol) can also produce compound 5i (2.1 mg), but the yield is only 20%. The structure of compound 5i was confirmed by X-ray single crystal diffraction. Fig. 9 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0386] 1 H NMR(600MHz,CDCl3,ppm)δ:The protons of C2H,C3H,C5H,C6H,C8H,C9H,C11H,C12H and C15H(totally 9H)resonant at 9.91(d,J(HH)=3.9Hz,1H),9.87(s,1H),9.49(m,2H),9.44(d,J(HH)=3.3Hz,1H),9.42(d,J(HH)=3.8Hz,1H),9.34(m,2H),and 9.26(d,J(HH)=3.5Hz,1H); 6.98(t,J(HH)=7.6Hz,6H,Hp of PPh3), 6.75 (t, J(HH) = 7.6 Hz, 12H, H m of PPh3), 5.48 (m, 12H, H o of PPh3).

[0387] 31 P{ 1 H} NMR (243 MHz, CDCl3, ppm) δ: -17.96 (s, OsPPh3).

[0388] 13 C{ 1 H} NMR (151 MHz, CDCl3, ppm) δ: The carbon atoms of C1, C4, C7, C10 and C13 (totally 5C) resonant at 205.8 (t, J(PC) = 6.7 Hz), 201.2 (t, J(PC) = 7.4 Hz), 200.0 (t, J(PC) = 7.3 Hz), 183.8 (t, J(PC) = 7.4 Hz), 182.9 (t, J(PC) = 7.1 Hz); The carbon atoms of C2, C3, C5, C6, C8, C9, C11, C12, C14 and C15 (totally 10C) resonant at 156.8 (s), 155.3 (s), 154.8 (s), 154.0 (s), 152.828 (s), 151.9 (s), 151.7 (s), 151.4 (s), 146.7 (s), 145.4 (s); 133.3 (t, J(PC) = 4.7 Hz, C o of PPh3), 130.8 (t, J(PC) = 25.1 Hz, CP of PPh3), 128.8 (s, C p of PPh3), 125.5 (t, J(PC) = 4.9 Hz, C m of PPh3).

[0389] HRMS (ESI): (m / z) [M + H] + calcd for 5i [C 51 H 40 OsNO2P2] + 952.2144, found 952.2144.

[0390] Example 21: Synthesis of Osmium

[15] annulene 5j

[0391]

[0392] In an argon atmosphere, 5d (10.0 mg, 0.011 mmol) was dissolved in chloroform (5 mL), and t-BuOCl (124 μL, 1.1 mmol) was added to the solution. After reacting at 42°C for 12 hours, the solution was concentrated to about 2 mL, and the residue was loaded into a 200-300 mesh silica gel column for column chromatography. Dichloromethane was used as the eluent to obtain an orange solid compound 5j (10.2 mg, yield 74%). The structure of compound 5j was confirmed by X-ray single crystal diffraction. Fig.10 This is the single crystal structure diagram. In addition, nuclear magnetic resonance 1 H. 31 P{ 1 H}, 13 C{ 1 H}NMR and high-resolution mass spectrometry HRMS confirmation. The specific NMR and high-resolution mass spectrometry characterization data of the compound are as follows:

[0393] 1 H NMR (600MHz, CDCl3, ppm) δ: 7.15 (t, J (HH) = 7.5Hz, 6H, H p of PPh3),7.01(t,J(HH)=7.5Hz,12H,H m of PPh3),5.60(dd,J(PH)=12.3Hz,J(HH)=5.5Hz,12H,H o ofPPh3).

[0394] 31 P{ 1 H}NMR(243MHz,CDCl3,ppm)δ:-16.89(s,OsPPh3).

[0395] 13 C{ 1 H}NMR (151MHz,CD2Cl2,plus 13 C-DEPT 135, 1 H- 13 C HSQC and 1 H- 13 C HMBC, ppm) δ: 161.3 (t, J (PC) = 6.3 Hz, OsC), 143.1 (s, CCl of annulene), 132.2 (t, J ( PC) = 4.5 Hz, C o of PPh3),130.1(s,C pof PPh3),128.7(t,J(PC)=25.8Hz,CP of PPh3),127.5(t,J(PC)=4.5Hz,C m of PPh3).

[0396] HRMS(ESI):(m / z)calcd for 5j[C 51 H 30 Cl 10 OsP2] + 1249.8264, found 1249.8236.

[0397] Example 22: Preparation of (E)-N-benzyl-1-phenylmethylamine by photocatalytic oxidative coupling reaction of benzylamine using the osmium

[15] annulene complex of the present invention

[0398] After successfully preparing a series of osmium

[15] annulene complexes with metal located at the center of the annulene plane, the inventors of the present invention found that they can catalyze the oxidative coupling reaction of benzylamine in CH2Cl2 solvent at room temperature under air atmosphere and blue light irradiation to prepare (E)-N-benzyl-1-phenylmethylamine. The specific experimental steps are as follows: Under air atmosphere, benzylamine (93 mg, 0.1 mmol) and catalyst (1 mol%) are dissolved in dichloromethane (5 mL), and then illuminated with a blue light LED lamp with an emission wavelength of 450-455 nm and a power of 40 watts. The reaction temperature is maintained at room temperature in a water bath. After reacting for 24 hours, it is concentrated under reduced pressure, and then 1,3,5-trimethoxybenzene (0.5 mmol) is added to the reaction tube as an internal standard, and then dissolved in CDCl3. 1 The yield of the product (E)-N-benzyl-1-phenylmethanamine was calculated by HNMR. The results are shown in Table 1.

[0399] Table 1: Preparation of (E)-N-benzyl-1-phenylmethylamine by photocatalytic oxidative coupling reaction of benzylamine with osmium

[15] annulene complex

[0400]

[0401]

[0402] It can be seen from the experimental results in the above table that the catalyst and the LED lamp are indispensable for the reaction. The osmium

[15] annulene complex of the present invention has good catalytic activity in the reaction of catalyzing the oxidative coupling of benzylamine to prepare (E) -N-benzyl-1-phenylmethylamine, especially

[55555] osmium

[15] annulene 5a has the best catalytic activity, and the yield can reach 85% after 24 hours of reaction.

[0403] The method of the present invention has been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.

Claims

1. A novel complex in which a metal is located at the center of the annulare plane, which is a [55753]metal[15]annulare of formula (I), a [55753]metal[15]annulare of formula (I'), a [55735]metal[15]annulare of formula (II), a [55663]metal[15]annulare of formula (III), a [55636]metal[15]annulare of formula (IV) or a [55555]metal[15]annulare of formula (V), wherein the five numbers in the square brackets represent the number of atoms in each small ring in the complex, counting clockwise from the five-membered ring in the lower right corner, and the two numbers in the other square brackets represent the number of carbon atoms in the annulare: in, M is Os or Ru; [M] is M(PPh3)2, M(PEt3)2, M(CO)2, M(PhNC)2 or M(BuNC)2; X is BPh4, F, Cl, Br or I; Each R 1a and R 2a and -C(=O)-(C1-C6 alkyl), -C(=O)-(C1-C6 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkyl substituted with hydroxy, C3-C8 cycloalkyl, 3-8 membered heterocyclyl, C6-C 10 aryl or 5-10 membered heteroaryl; and Each R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b and -C(=O)-(C1-C6 alkyl), -C(=O)-(C1-C6 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkyl substituted with hydroxy, C3-C8 cycloalkyl, 3-8 membered heterocyclyl, C6-C 10 Aryl or 5-10 membered heteroaryl.

2. The complex according to claim 1, wherein Each R 1a and R 2a and -C(=O)-(C1-C4 alkyl), -C(=O)-(C1-C4 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkyl substituted with hydroxy, C3-C6 cycloalkyl, 3-6 membered heterocyclyl, C6-C 10 aryl or 5-10 membered heteroaryl; and Each R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b and -C(=O)-(C1-C4 alkyl), -C(=O)-(C1-C4 alkoxy), p-toluenesulfonyl, trimethylsilyl, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkyl substituted with hydroxy, C3-C6 cycloalkyl, 3-6 membered heterocyclyl, C6-C 10 Aryl or 5-10 membered heteroaryl.

3. The complex according to claim 1 or 2, wherein Each R 1a and R 2a are independently H, F, Cl, Br, I, -CN, -NO2, -NH2, -OH, -SH, -COOH, -C(=O)NH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)-CH3, -C(=O)-OCH3, p-toluenesulfonyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, allyl, propenyl, propargyl, propynyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propyloxy, isopropyl oxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, -OCH2CF2CHF2, methylthio, ethylthio, methylamino, dimethylamino, ethylamino, hydroxymethyl, 2-hydroxyethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, azetidinyl, pyrrolidinyl, tetrahydrofuranyl, piperidinyl, piperazinyl, morpholinyl, phenyl, indenyl, naphthyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzimidazolyl, indolyl, or quinolinyl; and Each R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b are independently H, F, Cl, Br, I, -CN, -NO2, -NH2, -OH, -SH, -COOH, -C(=O)NH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)-CH3, -C(=O)-OCH3, p-toluenesulfonyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, allyl, propenyl, propargyl, propynyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propyloxy, isopropyl 1-Hydroxy, -OCHF, -OCF, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, -OCH2CF2CHF2, methylthio, ethylthio, methylamino, dimethylamino, ethylamino, hydroxymethyl, 2-hydroxyethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, azetidinyl, pyrrolidinyl, tetrahydrofuranyl, piperidinyl, piperazinyl, morpholinyl, phenyl, indenyl, naphthyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzimidazolyl, indolyl or quinolinyl.

4. The complex according to claim 1, which is [55753]osmium[15]annulene of formula (Ia), [55753]osmium[15]annulene of formula (I'-a), [55735]osmium[15]annulene of formula (II-a), [55663]osmium[15]annulene of formula (III-a), [55636]osmium[15]annulene of formula (IV-a) or [55555]osmium[15]annulene of formula (Va), wherein the five numbers in the square brackets represent the number of atoms in each small ring in the complex, counting clockwise from the five-membered ring in the lower right corner, and the two numbers in the other square brackets represent the number of carbon atoms in the annulene: in, [Os] is [Os]', [Os]", [Os]"', [Os]"" or [Os]""'; [Os]' is Os(PPh3)2, [Os]" is Os(PEt3)2, [Os]"' is Os(CO)2, [Os]"" is Os(PhNC)2, [Os]""' is Os(BuNC)2; X, R 1a , R 2a , R 1b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b Having the definition as claimed in claim 1.

5. The complex according to claim 4, wherein the [55753]osmium[15]annulene represented by formula (I'-a) is selected from the [55753]osmium[15]annulene represented by formula (I'-a-1): in, [Os] and R 1a Having the definition as claimed in claim 4.

6. The complex according to claim 4, wherein the [55735]osmium[15]annulene represented by formula (II-a) is selected from the [55735]osmium[15]annulene represented by formula (II-a-1): in, [Os]', R 1a and R 2a Having the definition as claimed in claim 4.

7. The complex according to claim 4, wherein the [55555]osmium[15]annulene represented by formula (Va) is selected from the [55555]osmium[15]annulene represented by formula (Va-1), the [55555]osmium[15]annulene represented by formula (Va-2) or the [55555]osmium[15]annulene represented by formula (Va-3): in, [Os]', [Os]”, R 1a and R 2a Having the definition as claimed in claim 4.

8. The complex according to claim 1 or 4, which is a complex having one of the following structures: in, [Os]′ and [Os]” have the definitions as set forth in claim 4.

9. The method for preparing the [55753]osmium[15]annulene of formula (Ia) according to claim 4, characterized in that: The method comprises the following steps: under inert gas conditions, reacting a compound represented by formula (I-a1) with a compound heating the reaction in an organic solvent, and after the reaction is completed, separating and purifying to obtain [55753]osmium[15]annulene represented by formula (Ia); Among them, [Os], X, R 1a and R 2a Having the definition as claimed in claim 4.

10. The method for preparing the [55753]osmium[15]annulene represented by formula (Ia) according to claim 9, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is 1,2-dichloroethane, dichloromethane, chloroform, tetrahydrofuran, methanol or toluene; The reaction temperature is 40-80°C; The reaction time is 8-18 hours; The compound represented by formula (I-a1) and the compound The molar ratio is 1:2~10.

11. The method for preparing the [55753]osmium[15]annulene represented by formula (I'-a) according to claim 4, characterized in that: The method comprises the following steps: under an inert gas condition, dissolving [55753]osmium[15]annulene represented by formula (Ia) in an organic solvent, adding KOH and reacting at room temperature, and after the reaction is completed, separating and purifying to obtain [55753]osmium[15]annulene represented by formula (I'-a); Among them, [Os], X, R 1a and R 2a Having the definition as claimed in claim 4.

12. The method for preparing the [55753]osmium[15]annulene of formula (I'-a) according to claim 11, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is 1,2-dichloroethane, methanol, dichloromethane, chloroform, tetrahydrofuran or toluene; Room temperature is 5-35℃; The reaction time is 1-6 hours; The molar ratio of [55753]osmium[15]annulene represented by formula (Ia) to KOH is 1:10-40.

13. The method for preparing the [55735]osmium[15]annulene of formula (II-a) according to claim 4, characterized in that: The method comprises the following steps: dissolving [55753]osmium[15]annulene represented by formula (I'-a) in an organic solvent under room temperature and air conditions, adding AlCl3 and Al2O3 and reacting at room temperature, and after the reaction is completed, separating and purifying to obtain [55735]osmium[15]annulene represented by formula (II-a); Among them, [Os], R 1a and R 2a Having the definition as claimed in claim 4.

14. The method for preparing the [55735]osmium[15]annulene represented by formula (II-a) according to claim 13, characterized in that: The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; Room temperature is 5-35℃; The reaction time is 8-18 hours; The molar ratio of [55753]osmium[15]annulene represented by formula (I'-a) to AlCl3 is 1:5 to 15; The molar ratio of AlCl3 to Al2O3 is 1:10-20.

15. The method for preparing the [55663]osmium[15]annulene of formula (III-a) according to claim 4, characterized in that: The method comprises the following steps: under inert gas conditions, dissolving [55753]osmium[15]annulene represented by formula (I'-a) in an organic solvent and heating for reaction, and after the reaction is completed, separating and purifying to obtain [55663]osmium[15]annulene represented by formula (III-a); Among them, [Os], R 1a and R 2a Having the definition as claimed in claim 4.

16. The method for preparing the [55663]osmium[15]annulene of formula (III-a) according to claim 15, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is tetrahydrofuran, dichloromethane, chloroform, 1,2-dichloroethane, methanol or toluene; The reaction temperature is 50-100°C; The reaction time is 60-120 hours.

17. The method for preparing the [55636]osmium[15]annulene of formula (IV-a) according to claim 4, characterized in that: The method comprises the following steps: under inert gas conditions, dissolving [55753]osmium[15]annulene represented by formula (I'-a-1) as claimed in claim 5 and 1-chloro-1,3-dihydro-3,3-dimethyl-1,2-benzoiodine oxolane in an organic solvent and reacting them at room temperature, and after the reaction is completed, separating and purifying to obtain [55636]osmium[15]annulene represented by formula (IV-a); Among them, [Os] and R 1a Having the definition as claimed in claim 4.

18. The method for preparing the [55636]osmium[15]annulene of formula (IV-a) according to claim 17, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is 1,2-dichloroethane, dichloromethane, chloroform, tetrahydrofuran, methanol or toluene; Room temperature is 5-35℃; The reaction time is 8-18 hours; The molar ratio of [55753]osmium[15]annulene represented by formula (I'-a-1) to 1-chloro-1,3-dihydro-3,3-dimethyl-1,2-benzoiodooxolane is 1:1-5.

19. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-1) according to claim 7, characterized in that: The method comprises the following steps: under inert gas conditions, dissolving the [55735]osmium[15]annulene of formula (II-a-1) as claimed in claim 6 in an organic solvent, adding an acid to the solution to react at room temperature, and after the reaction is completed, separating and purifying to obtain the [55555]osmium[15]annulene of formula (Va-1); Among them, [Os]', R 1a and R 2a Having the definition as claimed in claim 4.

20. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-1) according to claim 19, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; The acid is hydrochloric acid, tetrafluoroboric acid, hexafluorophosphoric acid or perchloric acid; Room temperature is 5-35℃; The reaction time is 8-18 hours; The molar ratio of [55735]osmium[15]annulene represented by formula (II-a-1) to the acid is 1:20 to 60.

21. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-2) according to claim 7, characterized in that: The method comprises the following steps: under inert gas conditions, dissolving the [55555]osmium[15]annulene represented by formula (Va-1) as claimed in claim 7 in an organic solvent, adding t-BuLi to the solution at low temperature, adding methanol to the solution to quench the reaction after the reaction is completed, and then separating and purifying to obtain the [55555]osmium[15]annulene represented by formula (Va-2); Among them, [Os]', R 1a and R 2a Having the definition as claimed in claim 4.

22. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-2) according to claim 21, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is tetrahydrofuran, dichloromethane, chloroform, 1,2-dichloroethane, methanol or toluene; The reaction temperature is -10 to -60°C; The reaction time is 5-60 minutes; The molar ratio of [55555]osmium[15]annulene represented by formula (Va-1) to t-BuLi is 1:3-10.

23. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-3) according to claim 7, characterized in that: The method comprises the following steps: under inert gas conditions, dissolving the [55555]osmium[15]annulene of formula (Va-2) described in claim 7 in an organic solvent, adding PEt3 to the solution, heating the solution for reaction, and separating and purifying after the reaction to obtain the [55555]osmium[15]annulene of formula (Va-3); Among them, [Os]', [Os]”, R 1a and R 2a Having the definition as claimed in claim 4.

24. The method for preparing the [55555]osmium[15]annulene represented by formula (Va-3) according to claim 23, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is 1,2-dichlorobenzene or diethylene glycol dimethyl ether; The reaction temperature is 150-250°C; The reaction time is 24-48 hours; The molar ratio of [55555]osmium[15]annulene represented by formula (Va-2) to PEt3 is 1:5-15.

25. The method for preparing [55555]osmium[15]annulene 5h according to claim 8, characterized in that: The method comprises the following steps: under an inert gas condition, dissolving [55555]osmium[15]annulene 5d in an organic solvent, adding ICl to the solution, reacting at room temperature, and separating and purifying to obtain [55555]osmium[15]annulene 5h after the reaction is completed; Wherein, [Os]' is Os(PPh3)2.

26. The method for preparing [55555]osmium[15]annulene 5h according to claim 25, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; Room temperature is 5-35℃; The reaction time is 6-24 hours; [55555]The molar ratio of osmium[15]annulene 5d to ICl is 1:5~15.

27. The method for preparing [55555]osmium[15]annulene 5i according to claim 8, characterized in that: The method comprises the following steps: under an inert gas condition, dissolving [55555]osmium[15]annulene 5d in an organic solvent, adding NO2BF4 or t-BuONO to the solution, reacting at room temperature, and separating and purifying to obtain [55555]osmium[15]annulene 5i after the reaction is completed; Wherein, [Os]' is Os(PPh3)2.

28. The method for preparing [55555]osmium[15]annulene 5i according to claim 27, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; Room temperature is 5-35℃; The reaction time is 6-24 hours; [55555]The molar ratio of osmium[15]annulene 5d to NO2BF4 or t-BuONO is 1:1 to 6.

29. The method for preparing [55555]osmium[15]annulene 5j according to claim 8, characterized in that: The method comprises the following steps: under an inert gas condition, dissolving [55555]osmium[15]annulene 5d in an organic solvent, adding t-BuOCl to the solution, heating the solution for reaction, and separating and purifying after the reaction is completed to obtain [55555]osmium[15]annulene 5j; Wherein, [Os]' is Os(PPh3)2.

30. The method for preparing [55555]osmium[15]annulene 5j according to claim 29, characterized in that: The inert gas is helium, neon, argon, krypton, xenon or radon; The organic solvent is chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; The reaction temperature is 30-60°C; The reaction time is 6-24 hours; The molar ratio of [55555]osmium[15]annulene 5d to t-BuOCl is 1:60 to 180.

31. Use of the novel metal complex at the center of the annulene plane according to any one of claims 1 to 8 in catalyzing the oxidative coupling reaction of benzylamine to prepare imines.

32. The use according to claim 31, characterized in that The method comprises the following steps: adding the novel metal complex located at the center of the annulene plane according to any one of claims 1 to 8, benzylamine and an organic solvent into a reactor under air atmosphere, and reacting them under light at room temperature to obtain a product (E)-N-benzyl-1-phenylmethylamine, and the reaction formula is as follows:

33. The use according to claim 32, characterized in that The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, methanol or toluene; Room temperature is 5-35℃; The light is blue light; The reaction time is 12-48 hours; The molar ratio of the novel metal complex located at the center of the annulene plane to benzylamine is 0.005-0.05:1.

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