DE102013016487B4 - Process for the preparation of metal-N-heterocyclic carbene complexes - Google Patents

Abstract

Process for the preparation of metal-N-heterocyclic carbene complexes (metal NHC complexes) by means of modular three-component template synthesis, comprising reacting a metal ligand compound MLmL'n with the formula (II), of a CH-acidic isocyanide having the general formula ( III) and an imine of the general formula (IV) .Where M is selected from Au, Rh, Ir or Ru, L and L 'are a ligand suitable for the respective metal, which by coordination also m and n, the number the ligand, where m and n are each 0, 1, 2, 3 or 4, Ar is selected from an unsubstituted, mono- or disubstituted phenyl group, wherein the substituents independently of one another from the group α consisting of a hydrogen atom, a straight-chain or branched-chain (C 1 -C 15) -alkyl radical, a (C 1 -C 15) -thioalkyl radical, a (C 3 -C 15) -cycloalkyl radical which may have one or more heteroatoms, a (C 1 -C 15) -alkoxy radical, a trifluoromethyl group, Bromine, chlorine and fluo Ar 'is selected from a straight-chain or branched-chain (C 1 -C 15) -alkyl radical or from an unsubstituted, monosubstituted or disubstituted phenyl group, where the substituents independently of one another are selected from the group consisting of a hydrogen atom, a straight-chain or branched-chain (C 1 -C 15) -alkyl radical, a (C 1 -C 15) -thioalkyl radical, a (C 3 -C 15) -cycloalkyl radical which may have one or more heteroatoms, a (C 1 -C 15) -alkoxy radical, a trifluoromethyl group, bromine, chlorine and fluorine, R is selected from a straight or branched chain, unsubstituted or substituted (C 1 -C 15) alkyl radical, where the substituents may be terminal phenyl radicals and the alkyl radicals may be linked by ether compounds, a (C 3 -C 15) cycloalkyl radical containing a or a plurality of heteroatoms, such as O or S, are selected from an unsubstituted, mono- or disubstituted phenyl or benzyl group, wherein the substituents independently are each selected from the group α, or R is an alkylene linker, which in turn terminally a group of formula (I) depends, or R is an alkylene linker at the terminal of a phosphine unit is present, which optionally metal-coordinated can be, ...

Description

The present invention relates to metal-N-heterocyclic carbene complexes (metal NHC complexes) and their synthesis. In contrast to classical syntheses, in the last reaction step, not the MC _carbene bond is attached, but in a modular three-component template synthesis the ring closure of the NHC is performed. This results in a high synthesis modularity. The complexes prepared according to the invention are usable in particular as catalysts.

N-heterocyclic carbenes (NHCs) are one of the most important ligand classes for transition-metal catalysts. But not only in catalysts, but also in liquid crystals, polymers, medical applications, electronically active materials, nanoparticles and supramolecular chemistry, self-assembly and photochemistry NHC complexes are used. Despite the large number of different applications, the synthesis of ligands and thus of NHC complexes remains a challenging task.

In the prior art, such metal-NHC complexes are usually prepared by preparing an NHC precursor followed by transmetallation; see. F.E. Hahn, ChemCatChem, 2013, 5, 419-430. However, such syntheses are not very modular. In addition, a high synthesis effort is required.

Rieger, D. et al., Inorg. Chim. Acta 1994, 222, pp. 275-290 discloses a novel reaction of metal-cyano complexes to provide an organometallic synthetic route to 4-aminoimidazoles by means of a four-component condensation of isocyanides, aldehydes and imines. Van Leusen, A.M. et al., J. Org. Chem. 1977, 42, pp. 1153-1159 discloses a base-mediated cycloaddition of sulfonylmethyl isocyanides to aldimines and imidoyl chlorides for the synthesis of differently substituted imidazoles. Hahn, F.E. et al., Chem. Eur. J. 2003, 9, pp. 704-712, discloses a template synthesis of benzannellated N-heterocyclic carbene ligands. Hahn, F.E. et al., Angew. Chem. Int. Ed. 2005, 44, p. 3759-3763) discloses the template synthesis of a coordinated tetracarbene ligand with crown ether topology. Hashmi, S.K. et al., Adv. Synth. Catal. 2010, 352, pp. 1315-1337, discloses the structures of open-chain gold (I) carbenes and their application in gold-catalyzed phenol synthesis and the hydration of alkynes.

The present invention is therefore based on the object to provide a synthesis method which should allow access to metal NHC complexes under mild conditions. In this case, a high modularity of the method should be ensured in order to ensure efficient applicability in (catalysis) screenings. Access to the organic reactants should be simple and effective, as this is the only prerequisite for the convenient synthesis of NHC complexes.

This object is achieved by the embodiments characterized in the claims.

wobei
M aus Au, Rh, Ir oder Ru ausgewählt ist,
L und L' ein für das jeweilige Metall geeigneter Ligand sind, welcher durch die Koordination auch m und n, die Anzahl der Liganden, vorgibt, wobei m und n jeweils 0, 1, 2, 3 oder 4 sind,
Ar aus einer un-, mono- oder disubstituierten Phenylgruppe ausgewählt ist, wobei die Substituenten unabhängig voneinander aus der Gruppe α, bestehend aus einem Wasserstoffatom, einem geradkettigen oder verzweigtkettigen (C₁-C₁₅)-Alkylrest, einem (C₁-C₁₅)-Thioalkylrest, einem (C₃-C₁₅)-Cycloalkylrest, der ein oder mehrere Heteroatome, wie beispielsweise O oder S, aufweisen kann, einem (C₁-C₁₅)-Alkoxyrest, einer Trifluormethylgruppe, Brom, Chlor und Fluor, vorzugsweise aus (C₁-C₆)-Alkyl, (C₁-C₆)-Alkoxy, Brom, Chlor und Fluor, ausgewählt sind,
Ar' aus einem geradkettigen oder verzweigtkettigen (C₁-C₁₅)-Alkylrest oder aus einer un-, mono- oder disubstituierten Phenylgruppe, vorzugsweise aus einer solchen un-, mono- oder disubstituierten Phenylgruppe, ausgewählt ist, wobei die Substituenten unabhängig voneinander aus der Gruppe α, bestehend aus einem Wasserstoffatom, einem geradkettigen oder verzweigtkettigen (C₁-C₁₅)-Alkylrest, einem (C₁-C₁₅)-Thioalkylrest, einem (C₃-C₁₅)-Cycloalkylrest, der ein oder mehrere Heteroatome, wie beispielsweise O oder S, aufweisen kann, einem (C₁-C₁₅)-Alkoxyrest, einer Trifluormethylgruppe, Brom, Chlor und Fluor, vorzugsweise aus (C₁-C₆)-Alkyl, (C₁-C₆)-Alkoxy, Brom, Chlor und Fluor, ausgewählt sind,
R aus einem geradkettigen oder verzweigtkettigen, unsubstituierten oder substituierten (C₁-C₁₅)-Alkylrest, wobei die Substituenten terminale Phenylreste sein können und die Alkylreste durch Etherverbindungen verknüpft sein können, einem (C₃-C₁₅)-Cycloalkylrest, der ein oder mehrere Heteroatome, wie beispielsweise O oder S, aufweisen kann, einer un-, mono- oder disubstituierten Phenyl- oder Benzylgruppe ausgewählt ist, wobei die Substituenten unabhängig voneinander aus der Gruppe α ausgewählt sind, oder
R für einen Alkylenlinker steht, an dem wiederum endständig eine Gruppe gemäß Formel (I) hängt, oder
R für einen Alkylenlinker steht, an dem endständig eine Phosphan-Einheit vorliegt, die gegebenenfalls Metall-, insbesondere Gold-koordiniert sein kann,
oder
Ar' und R zusammen unter Ringschluß für eine 3,4-Dihydroisochinolin-Einheit stehen, und
EWG für eine elektronenziehende Gruppe, insbesondere für eine R_EWG-SO₂-, eine Ester-, eine Phosphonat-, eine Benzotriazol- oder eine Nitro-Gruppe, vorzugsweise für R_EWG-SO₂-, steht, wobei R_EWG CF₃ (Triflyl) oder CH₃C₆H₅ (Tosyl) darstellt,
wodurch Metall-Imidazol-2-yliden-Komplexe gemäß der allgemeinen Formel (I) erhalten werden.In particular, there is provided a process for the preparation of metal-N-heterocyclic carbene complexes (metal-NHC complexes) by modular three-component template synthesis comprising reacting a metal ligand compound ML _m L ' _n with the formula (II), a CH-acid Isocyanide having the general formula (III) and an imine, preferably an arylimine, having the general formula (IV).

in which
M is selected from Au, Rh, Ir or Ru,
L and L 'are a ligand suitable for the respective metal, which by coordination also predetermines m and n, the number of ligands, where m and n are each 0, 1, 2, 3 or 4,
Ar is selected from an unsubstituted, monosubstituted or disubstituted phenyl group, wherein the substituents independently of one another from the group α, consisting of a hydrogen atom, a straight-chain or branched-chain (C ₁ -C ₁₅ ) alkyl radical, a (C ₁ -C ₁₅ ) Thioalkyl radical, a (C ₃ -C ₁₅ ) -cycloalkyl radical which may have one or more heteroatoms, such as, for example, O or S, a (C ₁ -C ₁₅ ) -alkoxy radical, a trifluoromethyl group, bromine, chlorine and fluorine, preferably selected from (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, bromine, chlorine and fluorine,
Ar 'is selected from a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical or from an unsubstituted, monosubstituted or disubstituted phenyl group, preferably from such an unsubstituted, monosubstituted or disubstituted phenyl group, where the substituents are independently of one another the group α consisting of a hydrogen atom, a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical, a (C ₁ -C ₁₅ ) -thioalkyl radical, a (C ₃ -C ₁₅ ) -cycloalkyl radical having one or more heteroatoms , such as O or S, a (C ₁ -C ₁₅ ) alkoxy, a trifluoromethyl group, bromine, chlorine and fluorine, preferably of (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) - Alkoxy, bromine, chlorine and fluorine, are selected,
R is selected from a straight-chain or branched-chain, unsubstituted or substituted (C ₁ -C ₁₅ ) -alkyl radical, where the substituents can be terminal phenyl radicals and the alkyl radicals can be linked by ether compounds, a (C ₃ -C ₁₅ ) -cycloalkyl radical which contains an or a plurality of heteroatoms, such as O or S, an unsubstituted, mono- or disubstituted phenyl or benzyl group is selected, wherein the substituents are independently selected from the group α, or
R is an alkylene linker to which in turn terminally a group according to formula (I) depends, or
R is an alkylene linker at the terminal of which there is a phosphine unit which may optionally be metal-coordinated, in particular gold-coordinated,
or
Ar 'and R together are ring-closed for a 3,4-dihydroisoquinoline moiety, and
EWG is an electron-withdrawing group, in particular an R _EWG -SO ₂ , an ester, a phosphonate, a benzotriazole or a nitro group, preferably for R _EWG -SO ₂ -, wherein R _EWG CF ₃ ( Triflyl) or CH ₃ C ₆ H ₅ (tosyl),
whereby metal-imidazol-2-ylidene complexes according to the general formula (I) are obtained.

In the template synthesis, the ring closure of the NHC ligand occurs after the formation of the MC _carbene bond. The key intermediates in this strategy are metal-isocyanide complexes. By coordination of an isocyanide to a metal, the C _isocyanide atom is more polarized, so that a ring closure is possible under mild conditions. Examples of template syntheses that do not involve an isonitrile intermediate are still unknown.

In the context of the method according to the invention was the M d3 / a1 + 2 pattern applied to meet the above-mentioned requirements of the synthesis.

The required CH-acidic isocyanides (see the above formula (III)) are either commercially available or can be easily synthesized. Thus, when, for example, tosylate is provided as the electron-withdrawing group, the isocyanides can be easily prepared from an aryl aldehyde, sulfinic acid and formamide to produce a formamide derivative and then reacting with POCl ₃ under dehydration. The imines (see formula (IV) above) can be synthesized in large quantities by a simple condensation reaction of aldehydes and primary amines.

Suitable metal ligand starting compounds (II) are the Au, Rh, Ir or Ru complexes known to the person skilled in the art. The ligands L and L 'and thus m and n are within the skill of the art. In addition to the classical ligands such as halides and cp (cyclopentadienyl) or cp * and Cymene also coordinating solvents such as THF, THT, DMS, etc. come into question.

For example, (THT) AuCl, (DMS) AuCl, (RhCl ₂ (cp *)) dimer, (IrCl ₂ (cp *)) dimer, [RuCl ₂ (cymene)] dimer can be used as metal ligand starting compound (II) , [RuCl ₂ (benzene)] - dimer or [RuCl ₂ (toluene)] - dimer can be used.

Suitable solvents for the synthesis process according to the invention in particular acetone, acetonitrile, benzene, toluene, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethane, diethyl ether, Diethylenglycoldimethylester, DME (1,2-dimethoxyethane), dimethylformamide, dimethyl sulfoxide, dioxane, ethyl acetate , Hexamethylphosphoramide, hexamethylphosphoric triamide, pentane, hexane, cyclohexane, methyl tert-butyl ether, N-methyl-2-pyrrolidinone, nitromethane, petroleum ether, tetrahydrofuran, toluene or xylenes.

For the development of the method according to the invention, the gold-isocyanide complexes were used as a model. These have the advantage that due to the linear coordination of the ligands on the gold, the reaction can not be suppressed by steric hindrance of other ligands. Also, in two-coordinate gold complexes there are no vacant coordination sites on the central atom at which side reactions could be catalyzed. In addition, no additional signals are present in the NMR spectra, which may possibly overlap with product signals.

In the context of the present invention, the synthesis of the gold NHC complexes 4 in a one-pot reaction could be realized. Preferably (THT) AuCl 1a or (DMS) AuCl 1b and an isocyanide 2a or 2b were stirred in acetonitrile for 1 h at room temperature. The precipitated as a white solid isocyanide complex dissolves immediately upon addition of an imine 3, after about 5 minutes as gold-NHC complex 4 again precipitate. In order to achieve complete conversion, the suspension is usually stirred for a further hour at room temperature.

Due to the modularity of the process according to the invention, gold complexes with various trisubstituted unsaturated NHC ligands can be synthesized in good to very good yields. The process of the invention allows access to NHC ligands with symmetrical (4a-f) and unsymmetrical (4g-h) Ar / Ar'-substituted backbone. In addition, the process according to the invention allows the N atom to carry linear (4c-d), branched (4a) and cyclic (4f) alkyl and aryl substituents (4b). However, annellated NHC ligands (4e) are also accessible in this way. In addition, the synthesis of dinuclear NHC / NHC (4i) and phosphine / NHC complexes (4j) is possible.

To prove that it is indeed a NHC template synthesis and not a heterocyclic synthesis, in addition to the mass spectrometry and NMR spectroscopy contribute. In the ¹ H NMR spectrum one finds a strongly downfield shifted (δ> 10 ppm) singlet, which shows no cross peaks in the HSQC. This is a clear indication of an NH group as it exists in the complexes 4a-j. In contrast, the heterocycle would have a singlet in the range δ = 8-10 ppm, which would also have a cross peak in the HSQC. Such a signal was not observed in any of the spectra. The signal at δ> 10 ppm can therefore be used as a marker for the synthesis or further implementation of trisubstituted NHC complexes.

The final proof that this is an NHC template synthesis and not an imidazole synthesis followed by Au-N coordination can be obtained by X-ray crystal structure analysis. The bond lengths and angles show the typical values of a gold-NHC complex. Due to the asymmetrical substitution pattern, however, there is a slight distortion of the NHC ring and a slight tilting of the NHC in the ring plane.

Although the isocyanide complexes of rhodium and iridium do not have sufficient activation for the "classical" template synthesis of NHC complexes, the rhodium and iridium NHC complexes can be prepared under adapted reaction conditions. Here, the rhodium and iridium isocyanide complexes are first prepared in a first step, which are then converted in a second step using an amine base, preferably triethylamine, in the rhodium and iridium NHC complexes. The rhodium and iridium-NHC complexes 7a-h and 8a-h are given below by way of example.

It should be noted that the actual NHC synthesis is generally followed by a ligand exchange reaction in which, for example, a chloro ligand is replaced by the tosylate anion formed in the reaction. With yields in the range of 66% to 89% for the NH / NR _alkyl- stabilized NHC complexes, the yield for the rhodium complexes 7a-h is slightly better than for the corresponding iridium complexes 8a-h (55-78%).

X-ray crystallographic analyzes of the rhodium / iridium NHC complexes clearly show that they are tetrahedral NHC complexes whose structures have the bond lengths and angles expected for this class of compounds. The tosylate ligand is coordinated to the metal via an S atom.

Ruthenium-NHC complexes 10a-f can also be synthesized by the metal despite the low CN activation. Again, first in a first step, the ruthenium-isocyanide complex is prepared, which is then converted in a second step using an amine base, preferably triethylamine, in a ruthenium-NHC complex.

X-ray crystallographic analyzes of the ruthenium-NHC complexes again show a tetrahedral coordination sphere with the newly formed NHC and one chloro, one Cymene, and one Ts ligand. The bond angles and lengths are also in the range typical of such compounds for these complexes.

As far as the reaction mechanism of the process according to the invention is concerned, it can be assumed that in the reaction of the gold-isocyanide complex there is sufficient activation of the CH-acidic proton in order to be deprotonated by an imine. Thus, in all cases, NHC template synthesis starts with the deprotonation of the CH-acidic proton to give A. Therefore, it is obvious that the course of the reaction, with the exception of the last reaction step, corresponds to the gold-catalyzed oxazole and imidazole synthesis according to Ito / Hayashi; see. Ito, M. Sawamura, T. Hayashi, J. Am. Chem. Soc. 1986, 108, 6405-6406. Instead of protodermetalation of C, in the last reaction step protonation of the N atom takes place to form D. The reason for the lack of protodesauration is probably due to the change from a cationic gold species [AuPR ₃ ] ⁺ to a neutral gold species [AuCl]. In the final reaction step, the product is formed by elimination of sulfinic acid (in the case of Ts as EWG).

In the context of the present invention, the trisubstituted NHC ligands were also converted into trimeric gold-NHC complexes. By way of example, mention is made of the gold NHC trimers 11a-c, which can be obtained in excellent yield.

According to the invention, the gold NHC trimers can also be converted into tetrasubstituted gold-NHC complexes. By way of example, starting from the gold NHC trimers 11a and 11b with trisubstituted NHC ligands, the tetrasubstituted gold NHC complexes 12a-c can be synthesized in an analogous strategy under adapted reaction conditions with very good yields (92-96%).

In order to investigate the catalytic activity of the metal-NHC complexes prepared according to the invention, the phenol synthesis starting from substrate 13a was chosen. First, various silver salts were tested to activate the catalyst 4a. For example, AgNTf ₂ proves to be favorable for this purpose. With all catalysts, this reaction proceeds until complete conversion of the starting material. The yield of product for the gold complexes with trisubstituted NHC ligands ranges between 51% and 69%. Only catalyst 4h with unsymmetrically substituted backbone on the NHC ligand achieves quantitative yield. The fourth substituent on the NHC increases the yield from 69% for 4a and 56% for 4c to 80% for 12b. The improvement in the yield of phenol 14b was lower with 69% for 4b to 73% for 12c than for 12b.

Tabelle 1: Ergebnisse der goldkatalysierten Phenolsynthese.

Noteworthy is the effect on selectivity when catalysis is started silver-free by adding HNTf ₂ to the trimers. For the gold-NHC complex with Ph substituents on the N atom (4b or 11b), there is no change in the catalysis result. However, when the ^j Pr-substituted (4a or 11a) or the fused (4e or 11c) complex is used, quantitative yield of the desired product is obtained.

Table 1: Results of the gold-catalyzed phenol synthesis.

The process of the invention provides a simple and modular approach to metal NHC complexes, where the template synthesis is independent of the activation of the CN group of the isocyanide in the precursor complexes. As a result, it is possible in a simple and advantageous manner to also produce metal NHC complexes which were not previously accessible via template synthesis. The process according to the invention not only allows the synthesis of gold, but also of rhodium, iridium and ruthenium-NHC complexes.

The gold-NHC complexes synthesized by the process according to the invention can be used as starting materials for cyclic gold NHC trimers and gold complexes with tetrasubstituted NHC ligands.

The metal-NHC complexes synthesized by the process according to the invention are suitable as catalyst, for example for phenol synthesis.

The invention is further illustrated by the following examples, without being limited thereto.

I. Gold Chemistry

General Procedure A: Synthesis of Au-NHC Complexes

In a typical protocol, (THT) AuCl (1 eq) and Ar-TosMIC (1 eq) were combined in MeCN (5 ml / 100 mg [Au]) and stirred at room temperature. After 1 hour, the imine (1 eq) was added and the mixture was stirred for an additional 1 hour at room temperature. After addition of 20 ml / (100 mg [Au]) of TBME, the product was filtered off and dried in vacuo. 1. Chloro (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (500 mg, 1.56 mmol), Ph-TosMIC (423 mg, 1.56 mmol) and N-benzylidene-2-propylamine (230 mg, 1.56 mmol).
Colorless solid: 752 mg (1.52 mmol, 97%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.70 (d, J = 6.7 Hz, 6H), 2.28 (s, 3H), 4.41 (sept, J = 6.7 Hz, 1H), 7.21-7.24 ( m, 2H), 7.26-7.30 (m, 3H), 7.34 (d, J = 7.3Hz, 2H), 7.48-7.56 (m, 3H), 10.65 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 24.26 (q, 2C), 50.97 (d), 126.95 (d, 2C), 128.26 (s), 128.44 (s), 128.68 (s), 128.88 (d), 129.29 (d, 2C), 129.71 (d, 2C), 129.87 (s), 130.31 (d), 131.67 (d, 2C), 163.66 (s); IR (KBr disc): υ~ = 3436, 2977, 2928, 1631, 1492, 1445, 1382, 1369, 1343, 1295, 1217, 1159, 1125, 1073, 1039, 770, 694, 573, 522, 436 cm ^{. 1} ; HR-MS (FAB (+)): m / z = 494.0802, calc'd for C ₁₈ H ₁₈ ClN ₂ Au [M] ^+:. 494.0824 2. chloro (1,4,5-triphenyl-imidazole-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (100 mg, 312 μmol), Ph-TosMIC (85 mg, 312 μmol) and N-benzylideneaniline (57 mg, 312 μmol).
Colorless solid: 128 mg (259 μmol, 83%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 7.09 (d, J = 8.0 Hz, 2H), 7.52 (t, J = 7.6 Hz, 2H), 7.29-7.43 (m, 11H), 11.49 ( s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 123.57 (d), 126.07 (d), 127.53 (d), 128.06 (d), 128.08 (s), 128.13 (s), 129.09 (d), 129.20 (d), 129.33 (d), 129.35 (d), 129.41 (d), 129.42 (d), 129.54 (d), 129.58 (s), 130.08 (d), 130.39 (s), 131.26 (d), 138.50 (s), 167.31 (s); IR (KBr disc): υ ~ = 3388, 3200, 3057, 1596, 1497, 1466, 1455, 1447, 1386, 1261, 1074, 1028, 916, 784, 763, 726, 693, 628, 616, 530 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 493.0927, calc'd for C ₂₁ H ₁₆ N ₂ Au [M-Cl ^{-] +:.} 493.0979. 3. Chloro (1-benzyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (DMS) AuCl (100 mg, 340 μmol), Ph-TosMIC (93 mg, 340 μmol) and N-benzylidenbenzylamine (66 mg, 340 μmol).
Colorless solid: 99 mg (182 μmol, 54%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 5.33 (s, 2H), 6.99 (d, J = 7.9 Hz, 1H), 6.99 (d, J = 7.1 Hz, 1H), 7.10-7.20 ( m, 5H), 7.25-7.29 (m, 3H), 7.29-7.34 (m, 2H), 7.37 (d, J = 7.4Hz, 1H), 7.39 (d, J = 7.4Hz, 1H), 7.46 (t , J = 7.4 Hz, 1H), 11.66 (s, 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 53.34 (t), 126.94 (d, 2C), 127.63 (d, 2C), 128.18 (s), 128.24 (s), 128.35 (s), 128.80 (d, 2C), 128.90 (d), 129.26 (d, 2C), 129.51 (d, 2C), 129.71 (d), 129.97 (s), 130.19 (d), 131.48 (d, 2C), 136.45 (s 167.16 (s); IR (KBr disc): υ ~ = 3198, 3060, 1952, 1632, 1604, 1595, 1493, 1469, 1448, 1410, 1388, 1353, 1332, 1277, 1187, 1125, 1074, 1035, 1011, 976, 919 , 766, 731, 697, 596, 571, 515, 492, 465 cm ^-1 ; HR-MS (FAB (+)): m / z = 507.1152, Calcd for C ₂₂ H18N ₂ Au [M-Cl ^{-] +:.} 507.1136. 4. Chloro (1-phenylethyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (100 mg, 312 μmol), Ph-TosMIC (85 mg, 312 μmol) and N-benzylidene-2-phenylethylamine (66 mg, 312 μmol).
Colorless solid: 114 mg (205 μmol, 66%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 3.02 (t, J = 7.6 Hz, 2H), 4.25 (t, J = 7.6 Hz, 2H), 6.92 (d, J = 7.4 Hz, 2H) , 7.14 (tt, J = 7.2, 1.4 Hz, 1H), 7.16 (d, J = 7.4 Hz, 2H), 7.19 (d, J = 7.4 Hz, 2H), 7.26-7.32 (m, 3H), 7.34- 7.37 (m, 2H), 7.48 (m, 2H), 7.53 (tt, J = 7.4, 1.4 Hz, 1H), 11.80 (s, 1H); ¹³ C NMR (300 MHz, CD ₂ Cl ₂ ): δ = 37.99 (t), 50.79 (t), 126.91 (d, 2C), 127.07 (d), 128.32 (s), 128.44 (s), 128.75 (i.e. ), 128.95 (d, 2C), 129.19 (d, 2C), 129.22 (d, 2C), 129.28 (s), 129.60 (s), 129.71 (d, 2C), 130.21 (d), 131.37 (d, 2C ), 137.57 (s), 166.01 (s); IR (KBr disc): υ~ = 3179, 3058, 3026, 2943, 1603, 1595, 1492, 1470, 1452, 1407, 1389, 1357, 1157, 1074, 1030, 769, 698, 604, 515, 501 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 556.0903, calc'd for C ₂₃ H ₂₀ ClN ₂ Au [M] ^+. 556.0981. 5. Chloro (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (100 mg, 312 mol), Ph-TosMIC (85 mg, 312 μmol) and 3,4-dihydroisoquinoline (41 mg, 312 μmol).
Colorless solid: 136 mg (284 μmol, 91%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 3.16 (t, J = 6.5 Hz, 2H), 4.43 (t, J = 6.5 Hz, 2H), 7.12 (t, J = 7.5, 1H), 7.26 (t, J = 7.5, 1H), 7.31 (dd, J = 7.5, 1H), 7.40 (d, J = 7.5, 1H), 7.48-7.55 (m, 3H), 7.61 (dd, J = 7.5, 1.4 Hz, 2H), 10.69 (s, 1H); ¹³ C NMR (300 MHz, CD ₂ Cl ₂ ): δ = 29.61 (t), 46.83 (t), 124.41 (d), 124.12 (s), 125.75 (s), 127.57 (d), 127.69 (s). 128.73 (d, 2C), 128.89 (s), 128.99 (d), 129.05 (d), 129.74 (d, 2C), 130.03 (d), 134.10 (s), 164.89 (s); IR (KBr disc): υ ~ = 3397, 3210, 3057, 2940, 1598, 1486, 1471, 1456, 1418, 1345, 1313, 1034, 764, 752, 728, 699, 672, 599, 570, 493 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 443.0840, calc'd for C ₁₇ H ₁₄ N ₂ Au [M-Cl ^{-] +:.} 443.0823. 6. Chloro (1-cyclohexyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (100 mg, 312 μmol), Ph-TosMIC (85 mg, 312 μmol) and N-benzylidene-cyclohexylamine (59 mg, 312 μmol).
Colorless solid: 120 mg (224 μmol, 72%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.17 (q, J = 13.0 Hz, 2H), 1.62 (d, J = 13.0 Hz, 2H), 1.85 (d, J = 13.0 Hz, 2H) , 1.95 (d, J = 13.0 Hz, 2H), 2.69 (q, J = 12.3 Hz, 2H), 3.88 (t, J = 12.3 Hz, 1H), 7.19-7.23 (m, 2H), 7.27-7.33 ( m, 2H), 7.48-7.56 (m, 2H), 10.47 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 25.38 (t), 26.40 (t), 30.08 (t), 35.06 (t), 58.53 (d), 127.00 (d, 2C), 128.24 (s ), 128.27 (s), 128.57 (s), 128.90 (d), 129.30 (d, 2C), 129.72 (d, 2C), 130.06 (d), 130.30 (s), 131.54 (d, 2C), C _carbene is missing; IR (KBr disc): υ~ = 3402, 3212, 3057, 2931, 2853, 1604, 1595, 1492, 1470, 1446, 1359, 1346, 1206, 1073, 1032, 970, 893, 769, 700, 614 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 499.1454, calc'd for C ₂₁ H ₂₂ N ₂ Au [M-Cl ^{-] +:.} 499.1449. 7. Chloro (5- (4-bromophenyl) -1-isopropyl-4-phenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (THT) AuCl (100 mg, 312 μmol), Ph-TosMIC (85 mg, 312 μmol) and N-4-bromobenzylidene-isopropylamine (71 mg, 312 μmol).
Colorless solid: 145 mg (253 μmol, 81%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.70 (d, J = 6.9 Hz, 6H), 4.39 (sept, J = 6.9 Hz, 1H), 7.20-7.23 (m, 4H), 7.30- 7.34 (m, 3H), 7.66 (d, J = 7.9 Hz, 2H), 10.53 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 23.90 (q), 50.79 (d), 124.48 (s), 126.69 (d, 2C), 127.27 (s), 127.54 (s), 128.24 (s ), 128.45 (s), 128.78 (d), 129.08 (d, 2C), 123.71 (d, 2C), 132.95 (d, 2C), C _carbene is absent; IR (KBr disc): υ~ = 3432, 2975, 2925, 1630, 1491, 1445, 1369, 1337, 1218, 1157, 1125, 1099, 1071, 1029, 1011, 832, 770, 695, 573, 505 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 537.0252 for C ₁₈ H ₁₇ BrN ₂ Au [M-Cl ^{-] +:.} 537.0241. 8. Chloro (1-isopropyl-4- (4-methoxyphenyl) -5-phenyl-imidazol-2-ylidene) gold (I)

According to Method A, the indicated compound was synthesized from (DMS) AuCl (100 mg, 339 μmol), Ph-TosMIC (103 mg, 339 μmol) and N-4-bromobenzylidene-isopropylamine (50 mg, 339 μmol).
Reddish-brown solid: 118 mg (224 μmol, 66%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.67 (d, J = 6.9 Hz, 6H), 3.75 (s, 3H), 4.40 (sept, J = 6.9 Hz, 1H), 6.80 (d, J = 8.9Hz, 2H), 7.22 (d, J = 8.9Hz, 2H), 7.30-7.35 (m, 2H), 7.49-7.52 (m, 2H), 7.69-7.74 (m, 1H), 11.55 (s , 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 24.25 (q, 2C), 50.80 (d), 55.62 (q), 114.54 (d, 2C), 120.82 (s), 126.19 (d), 128.50 (d, 2C), 128.73 (s), 129.20 (s), 129.64 (d, 2C), 130.10 (s), 131.81 (d, 2C), 160.01 (s), 162.31 (s); IR (KBr disc): υ ~ = 3571, 3489, 3436, 3256, 3233, 3066, 2976, 2932, 2837, 1608, 1574, 1520, 1497, 1463, 1371, 1300, 1248, 1213, 1183, 1126, 1070, 1032, 837, 815, 776, 736, 707, 684 601, 569, 529, 470 cm ^-1 ; HR-MS (FAB (+)): m / z = 489.1261, calc. for C ₁₉ H ₂₀ ON ₂ Au [M] ⁺ : 489.1241. 9. Dichloro (4,4 ', 5,5'-tetraphenyl-3,3'-propylene-diimidazol-2-ylidene) -digold (I)

According to Method A, the indicated compound was prepared from (THT) AuCl (100 mg, 312 μmol), Ph-TosMIC (85 mg, 312 μmol), and N ¹ , N ³ -dibenzylidenepropyl-1,3-diamine (39 mg, 156 μmol).
Colorless solid: 123 mg (130 μmol, 83%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 2.08 (quint., J = 7.2 Hz, 2H), 4.08 (t, J = 7.2 Hz, 4H), 7.13 (d, J = 7.9 Hz, 1H ), 7.31-7.36 (m, 5H), 7.38-7.44 (m, 4H), 7.46-7.52 (m, 4H), 7.53-7.59 (m, 5H), 7.31-7.36 (m, 5H), 7.67 (i.e. , J = 7.9 Hz, 1H), 13.35 (s, 2H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 32.63, 46.35, 126.37, 127.46, 128.61, 128.67, 128.67, 128.92, 129.28, 129.57, 129.84, 130.11, 130.47, 131.74, 138.42, 147.00, 167.00; IR (KBr disc): υ~ = 3429, 3161, 3054, 1631, 1598, 1493, 1449, 1409, 1173, 1124, 1096, 1037, 1011, 814, 769, 697, 650, 587, 570, 504 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 909.1406 calcd for C ₃₃ H ₂₈ ClN ₄ Au ₂ [M-Cl ^{-] +:.} 909.1334. 10. Dichloro (3- (2- (diphenylphosphino) ethyl) -4,5-diphenyl-diimidazol-2-ylidene) -digold (I)

According to Method A, the indicated compound was synthesized from (DMS) AuCl, Ph-TosMIC and a concurrently prepared solution of AuCl (N-benzylidene-2- (diphenylphosphino) ethanamine). The solution of AuCl (N-benzylidene-2- (diphenylphosphino) -ethanamine) was prepared by stirring (DMS) AuCl and N-benzylidene-2- (diphenylphosphino) ethanamine in 3 ml of MeCN at room temperature for 1 hour. The resulting solution was transferred to the reaction flask without purification.
Colorless solid: 105 mg (117 μmol, 46%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 2.89-3.02 (m, 2H), 4.26-4.46 (m, 2H), 7.23-7.37 (m, 6H), 7.41-7.71 (m, 14H) , 11.68 (s, 1H); IR (KBr disc): υ~ = 3419, 3215, 3055, 2224, 1967, 1635, 1595, 1559, 1540, 1492, 1448, 1436, 1405, 1358, 1336, 1159, 1122, 1104, 1073, 1037, 1012 , 998, 975, 920, 858, 814, 769, 742, 693, 649, 572, 536, 521 cm ^-1 ; HR-MS (FAB (+)): m / z = 861.0740 calcd for C ₂₉ H ₂₅ ClN ₂ PAu ₂ [M-Cl ^{-] +:.} 861.0775. General Procedure B: Synthesis of Au-NHC Trimers

In a typical protocol, a trisubstituted Au-NHC complex was dissolved in DCM and NEt ₃ was added. After stirring for 30 minutes, the reaction was quenched with water. The organic layer was separated, dried with MgSO ₄ and the solvent was removed under reduced pressure at room temperature. The resulting solid was purified by recrystallization in DCM / pentane. 1. (1-Isopropyl-4,5-diphenyl-imidazol-2-ylidenate) gold (I) trimer

According to Method B, the indicated compound was synthesized from chloro (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I) (500 mg, 1.01 mmol).
White solid: 452 mg (329 μmol, 98%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.38 (d, J = 6.9 Hz, 18H), 4.24 (sept, J = 6.9 Hz, 3H), 7.16-7.26 (m, 15H), 7.32- 7.40 (m, 9H), 7.48-7.53 (m, 6H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 24.35 (q, 6C), 49.56 (d, 3C), 127.14 (d, 3C), 128.35 (d, 6C), 128.53 (d, 3C), 128.79 (d, 6C), 130.06 (d, 6C), 130.41 (s, 3C), 131.84 (d, 6C), 131.94 (s, 3C), 134.21 (s, 3C), 136.81 (s, 3C), 165.31 (s, 3C); IR (KBr disc): υ ~ = 2969, 2926, 1676, 1602, 1501, 1483, 1443, 1382, 1366, 1344, 1311, 1292, 1274, 1178, 1105, 1073, 1022, 779, 769, 698 cm ^{- 1} ; HR-MS (FAB (+)): m / z = 1375.3162 calcd for C ₅₄ H ₅₂ N ₆ Au ₃ [M + H ⁺ ] ⁺ : 1375.3250. 2. (1,4,5-Triphenyl-imidazol-2-ylidenate) gold (I) trimer

According to Method B, the indicated compound was synthesized from chloro (1,4,5-triphenyl-imidazol-2-ylidene) gold (I) (140 mg, 264 μmol).
White solid: 125 mg (85 μmol, 96%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 6.86-6.91 (m, 4H), 7.04-7.11 (m, 5H), 7.13-7.17 (m, 3H), 7.21 (t, J = 7.5 Hz , 1H), 7.29 (d, J = 7.5 Hz, 2H); ¹³ C NMR (300 MHz, CD ₂ Cl ₂ ): δ = 127.19 (d, 3C), 127.75 (d, 3C), 128.06 (d, 3C), 128.07 (d, 6C), 128.29 (d, 6C), 128.32 (d, 6C), 128.77 (d, 6C), 129.06 (d, 6C), 131.03 (s, 3C), 131.04 (s, 3C), 131.15 (d, 6C), 132.83 (s, 3C), 137.87 (s, 3C), 138.98 (s, 3C), 169.20 (s, 3C); IR (KBr disc): υ~ = 3421, 3060, 1599, 1499, 1445, 1381, 1359, 1316, 1275, 1075, 1011, 912, 787, 764, 695, 646, 546 cm ^-1 ; HR-MS (FAB (+)): m / z = 1477.2745 calcd for C ₆₃ H ₄₆ N ₆ Au ₃ [M + H ⁺ ] ⁺ : 1477.2781. 3. (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidenate) gold (I) trimer

According to Method B, the indicated compound was synthesized from chloro (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidenes) gold (I) (100 mg, 209 μmol).
White solid: 87 mg (64 μmol, 95%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 3.05 (t, J = 6.3 Hz, 2H), 4.08 (t, J = 6.3 Hz, 2H), 7.03 (t, J = 7.6 Hz, 1H) , 7.12 (t, J = 7.6 Hz, 1H), 7.24 (d, J = 7.6 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.42-7.49 (m, 3H), 7.88 (d, J = 7.2 Hz, 2H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 30.32 (t), 44.70 (t), 123.99 (d), 125.65 (s), 127.05 (d), 127.09 (d), 128.38 (d), 128.48 (d), 128.61 (s), 128.61 (d, 2C), 130.19 (d, 2C), 133.67 (s), 134.81 (s), 135.69 (s), 167.43 (s); IR (KBr disc): υ~ = 3048, 2942, 2881, 1946, 1606, 1588, 1498, 1472, 1457, 1443, 1411, 1396, 1355, 1336, 1295, 1273, 1241, 1187, 1155, 1073, 1058 , 1028, 1003, 996, 927, 869, 788, 766, 753, 733, 700, 679, 653, 623, 581, 536, 497, 474, 436 cm ^-1 ; HR-MS (FAB (+)): m / z = 1327.2332, calcd for C ₅₁ H ₄₀ N ₆ Au ₃ [M + H ⁺ ] ⁺ : 1327.2311. General Procedure C: Synthesis of tetrasubstituted Au-NHC complexes

In a typical protocol, the Au-NHC trimer was stirred in 3 ml of alkyl halide at 80 ° C for 16 hours. Subsequently, the alkyl halide was removed under reduced pressure. The resulting solid was purified by column chromatography on SiO ₂ (PE / EA 5: 1). 1. Chloro (1-ethyl-2-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method C, the indicated compound was synthesized from (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I) trimer (100 mg, 73 μmol) and iodoethane.
White solid: 127 mg (207 μmol, 95%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.32 (t, J = 7.3 Hz, 3H), 1.73 (d, J = 6.9 Hz, 6H), 4.22 (q, J = 7.3 Hz, 2H), 4.47 (sept. J = 6.9Hz, 1H), 7.19-7.28 (m, 4H), 7.32-7.41 (m, 6H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 17.05 (q), 24.39 (q, 2C), 45.31 (t), 51.22 (d), 128.35 (s), 128.53 (d), 129.04 (i.e. , 2C), 129.08 (d, 2C), 129.58 (d), 129.69 (s), 130.58 (s), 131.05 (d, 2C), 131.48 (d, 2C), 131.70 (s), 178.21 (s); IR (KBr disc): υ ~ = 3055, 2972, 2924, 2854, 1725, 1631, 1502, 1487, 1461, 1444, 1410, 1379, 1368, 1334, 1272, 1206, 1179, 1158, 1116, 1075, 1050 , 1023, 964, 928, 892, 807, 766, 756, 701, 655, 591, 531, 507 cm ^-1 ; HR-MS (FAB (+)): m / z = 487.1420 calcd. For C ₂₀ H ₂₂ N ₂ Au [MI ^- ] ⁺ : 487.1449. 2. Chloro (1-benzyl-2-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I)

According to Method C, the indicated compound was synthesized from (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) gold (I) trimer (100 mg, 73 μmol) and benzyl bromide.
White solid: 131 mg (208 μmol, 96%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.76 (d, J = 6.8 Hz, 6H), 4.53 (sept, J = 6.8 Hz, 1H), 5.45 (s, 2H), 6.99-7.05 ( m, 4H), 7.19-7.27 (m, 7H), 7.28-7.41 (m, 4H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 24.43 (q, 2C), 51.58 (d), 53.84 (t, solvent overlay), 127.72 (d, 2C), 128.07 (s), 128.29 (i.e. , 2C), 128.37 (d), 128.88 (d, 2C), 128.96 (d), 129.62 (d, 2C), 129.78 (s), 131.18 (d), 131.24 (d, 2C), 131.49 (d, 2C ), 132.46 (s), 136.54 (s), 172.35 (s); IR (KBr disc): υ ~ = 3058, 2977, 2925, 1634, 1496, 1487, 1446, 1410, 1386, 1368 1335, 1253, 1202, 1180, 1157, 1117, 1076, 1051, 1024, 1014, 922, 832, 766, 736, 701, 654, 618, 576, 531, 458 cm ^-1 ; HR-MS (FAB (+)): m / z = 628.0738, calc'd for C ₂₅ H ₂₄ N ₂ AuBr [M] ^+. 628.0788. 3. Chloro (1-ethyl-2,4,5-triphenyl-imidazol-2-ylidene) gold (I)

According to Method C, the indicated compound was synthesized from (1,4,5-triphenylimidazol-2-ylidene) gold (I) trimer (100 mg, 68 μmol) and iodoethane.
White solid: 121 mg (187 μmol, 92%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.37 (t, J = 7.2 Hz, 3H), 4.27 (q, J = 7.2 Hz, 2H), 6.91-6.96 (m, 2H), 7.08- 7.14 (m, 2H), 7.19 (t, J = 7.4, 1.2 Hz, 1H), 7.31-7.49 (m, 10H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 16.66 (q), 44.27 (t), 127.51, 127.64, 127.70, 128.20, 128.55, 128.99, 129.05, 129.09, 129.23, 129.64, 130.40, 130.89, 131.11 , 131.63, 136.17 (s), 180.41 (s); IR (KBr disc): υ ~ = 3054, 2978, 2930, 1959, 1634, 1597, 1498, 1487, 1460, 1444, 1416, 1394, 1348, 1281, 1180, 1157, 1112, 1075, 1024, 918, 808 , 795, 777, 752, 695, 649, 532 cm ^-1 ; HR-MS (FAB (+)): m / z = 521.1281 for C ₂₃ H ₂₀ N ₂ Au [MI ^{-] +:.} 521.1292.

II. Rhodium Chemistry

General Procedure D: Synthesis of Rh Isocyanide Complexes

In a typical protocol, [RhCl ₂ (cp *)] ₂ and the isocyanide were dissolved in DCM and stirred at room temperature for 2 hours. Then the solvent was removed under reduced pressure. The resulting solid was the analytically pure isocyanide complex. 1. Dichloro (cp *) (Ph-TosMIC) rhodium (III)

According to Method D, the indicated compound was synthesized from [RhCl ₂ (cp *)] ₂ (250 mg, 431 μmol) and Ph-TosMIC (222 mg, 862 μmol).
Orange solid: 472 mg (862 mmol, quantitative); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.80 (s, 15H), 2.43 (s, 3H), 6.02 (s, 1H), 7.25-7.37 (m, 6H), 7.41-7.46 (m , 1H), 7.56-7.59 (m, 2H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 9.68 (q, 5C), 21.98 (q), 78.89 (d), 101.52 (s, d: J _{c, Rh} = 7.0, 5C), 127.08 ( s), 128.50 (d, 2C), 129.31 (d, 2C), 130.16 (s), 130.69 (d, 2C), 130.84 (d, 2C), 131.21 (d), 147.46 (s), C _CN is absent; IR (KBr disc): υ~ = 2918, 2182, 1696, 1595, 1522, 1495, 1456, 4375, 1334, 1157 1084 1025, 816, 782, 748, 700, 671, 639, 575, 549, 510, 480 cm ^-1 ; HR-MS (ESI (+)): m / z = 544.0588 calcd. For C ₂₅ H ₂₈ ClNO ₂ RhS [M-Cl ^- ] ⁺ : 544.0584. 2. Dichloro (cp *) (p-MeO-C ₆ H ₄ -TosMIC) rhodium (III)

According to Method D, the indicated compound was synthesized from [RhCl ₂ (cp *)] ₂ (153 mg, 248 μmol) and p-MeO-C ₆ H ₄ -TosMIC (150 mg, 496 μmol).
Orange solid: 303 mg (496 μmol, quantitative); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.80 (s, 15H), 2.44 (s, 3H), 3.80 (s, 3H), 5.91 (s, 3H), 6.86 (d, J = 8.8 Hz, 2H), 7.18 (d, J = 8.8 Hz, 2H) 7.33 (d, J = 8.2 Hz, 2H), 7.59 (d, J = 8.2 Hz, 2H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 9.64 (q, 5C), 21.95 (q), 55.81 (q), 78.45 (d), 101.41 (s, d: J _{c, Rh} = 7.0, 5C), 114.63 (d, 2C), 129.97 (d, 2C), 130.19 (s), 130.53 (d, 2C), 130.78 (d, 2C), 132.16 (s), 147.28 (s), 161.97 (s) , C _CN is missing; IR (KBr disc): υ ~ = 2914, 2180, 1608, 1595, 1514, 1453, 1376, 1333, 1309, 1293, 1257, 1180, 1155, 1083, 1025, 839, 815, 772, 712, 660, 596 , 569, 519, 458 cm ^-1 . 3. Dichloro (cp *) (methyl isocyano (phenyl) acetate) rhodium (III)

According to Method D, the indicated compound was synthesized from [RhCl ₂ (cp *)] ₂ (100 mg, 162 μmol) and methyl isocyano (phenyl) acetate (57 mg, 324 μmol).
Orange solid: 157 mg (324 μmol, quantitative); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.76 (s, 15H), 3.81 (s, 3H), 5.74 (s, 1H), 7.44-7.49 (m, 3H), 7.49-7.53 (m , 2H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.49 (q, 5C), 54.43 (q), 63.00 (d), 100.76 (s, d: J _{c, Rh} = 7.0, 5C), 127.19 ( d, 2d), 129.81 (d, 2C), 130.36 (d), 131.45 (s), 166.07 (s), C _CN absent; IR (KBr disc): υ~ = 2987, 2909, 2201, 1755, 1634, 1455, 1375, 1255, 1161, 1081, 1024, 738, 700, 588 cm ^-1 . 4. Dichloro (cp *) (diphenylmethyl isocyano) rhodium (III)

According to Method D, the indicated compound was synthesized from [RhCl ₂ (cp *)] ₂ (160 mg, 259 μmol) and diphenylmethyl isocyanide (100 mg, 517 μmol).
Orange solid: 260 mg (517 μmol, quantitative); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.67 (s, 15H), 6.24 (s, 1H), 7.32-7.49 (m, 10H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.51 (q, 5C), 64.94 (d), 100.31 (s, d: J _{C, Rh} = 7.0, 5C), 126.97 (d, 2C), 129.30 (s), 129.62 (d, 2C); 137.44; IR (KBr disc): υ~ = 3035, 2986, 2915, 2199, 1631, 1494, 1452, 1377, 1157, 1080, 969, 855, 749, 703, 652, 612, 558, 466 cm ^-1 ; HR-MS (ESI (+)): m / z = 466.0810 for C ₂₄ H ₂₆ ClNRh [M-Cl ^{-] +:.} 466.0809. General Procedure E: Synthesis of Rh NHC Complexes

In a typical protocol, RhCl ₂ (cp *) (Ar-TosMIC) (172 μmol), imine (172 μmol) and NEt ₃ (100 μl / μmol [Rh]) were dissolved in 5 ml of MeCN. After stirring at room temperature for 12 hours, the solution was quenched with 20 mL of water, separated, and the water phase was extracted with DCM (3 × 10 mL). The combined organic phases were dried with MgSO ₄ and the solvent was removed under reduced pressure. The resulting solid was purified by recrystallization in DCM / Et ₂ O. 1. Dichloro (cp *) (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and N-benzylidene-2-propylamine (26 mg, 172 μmol).
Orange solid: 106 mg (153 μmol, 89%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.01 (d, J = 7.0 Hz, 3H), 1.179 (d, J = 7.0 Hz, 3H), 1.63 (s, 15H), 2.31 (s, 3H), 5.19 (sept, J = 7.0 Hz, 1H), 7.04 (d, J = 8.2 Hz, 2H), 7.15-7.21 (m, 2H), 7.24-7.29 (m, 3H), 7.35 (d, J = 8.2 Hz, 2H), 7.39 (dd, J = 7.9, 1.5 Hz, 2H), 7.45-7.56 (m, 3H), 11.99 (s, 1H); IR (KBr disc): υ~ = 3058, 2975, 2918, 1632, 1507, 1489, 1457, 1369, 1352, 1232, 1176, 1087, 1026, 1010, 965, 812, 770, 707, 694, 634, 575 , 508 cm ^-1 ; HR-MS (ESI (+)): m / z = 713.1461, calc'd for C ₃₅ H ₄₅ ClN ₂ O ₂ RhSNa [M + Na ^{+] +:.} 713.1452. 2. Dichloro (cp *) (5- (4-bromophenyl) -1-isopropyl-4-phenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and Np-bromobenzylidene-2-propylamine (26 mg, 172 μmol).
Orange solid: 16 mg (21 μmol, 12%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.02 (d, J = 6.7 Hz, 3H), 1.19 (d, J = 7.2 Hz, 3H), 1.61 (s, 15H), 2.31 (s, 3H), 5.25-5.31 (m, 1H), 7.04 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 7.5 Hz, 2H), 7.26-7.34 (m, 5H), 7.37 (d, J = 8.0 Hz, 2H), 7.61-7.67 (m, 2H), 11.98 (s, 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.44 (q, 5C), 21.48 (q), 23.15 (q), 25.28 (q), 54.66 (d), 101.17 (s, d: J _{C , Rh} = 5.5Hz, 5C), 124.89 (s), 126.43 (d, 2C), 126.99 (d, 2C), 128.12 (d, 2C), 128.66 (s), 128.90 (d), 129.34 (s), 129.56 (s), 129.62 (d, 2C), 130.80 (s), 132.60 (d, 2C), 132.95 (s), 135.06 (d, 2C), 140.42 (s), 150.97 (s, d: J _{C, Rh} = 55.3 Hz); IR (KBr disc): υ ~ = 2972, 2917, 1698, 1635, 1558, 1541, 1507, 1486, 1456, 1366, 1232, 1162, 1075, 1023, 1011, 965, 834, 770, 693, 633, 576 , 509 cm ^-1 ; HR-MS (ESI (+)):. M / z = 769.0771, calc'd for C ₃₅ H ₄₀ N ₂ O ₂ RhS ³⁵ Cl Br ⁷⁹ [M + H ^{+] +:} 769.0732. 3. Dichloro (cp *) (1-benzyl-4,5-diphenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and N-benzylidenbenzylamine (34 mg, 172 μmol).
Orange solid: 92 mg (124 μmol, 72%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.63 (s, 15H), 2.40 (s, 3H), 4.70 (d, J = 14.3 Hz, 1H), 6.01 (d, J = 14.3 Hz, 1H), 6.26 (d, J = 7.6 Hz, 2H), 6.80-6.85 (m, 4H), 7.01 (t, J = 7.4 Hz, 1H), 7.11 (d, J = 8.0 Hz, 2H), 7.22 ( t, J = 7.3 Hz, 2H), 7.29-7.34 (m, 6H), 7.57 (d, J = 8.2 Hz, 2H), 12.35 (s, 1H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 9.35 (q, 5C), 21.63 (q), 52.36 (t), 101.31 (s, d: J _{c, Rh} = 5.5 Hz, 5C), 126.13 (d, 3C), 127.39 (d), 127.70 (d, 2C), 127.96 (d, 2C), 128.28 (d, 2C), 128.31 (d, 2C), 128.65 (s), 128.87 (s), 129.21 (d, 2C), 129.59 (d, 3C), 129.73 (s), 131.33 (d, 2C), 131.72 (s), 133.41 (s), 137.35 (s), 140.53 (s), 150.70 (s, d : J _{C, Rh} = 54.7 Hz); IR (KBr disc): υ ~ = 3449, 3059, 2976, 2916, 1634, 1598, 1491, 1452, 1400, 1378, 1355, 1173, 1109, 1085, 1027, 1009, 974, 810, 763, 731, 699 , 636, 575, 509 cm ^-1 ; HR-MS (ESI (+)): m / z = 739.1642, calc. For C ₃₉ H ₄₁ ClN ₂ O ₂ RhS [M + H ⁺ ] ⁺ : 739.1627. 4. Dichloro (cp *) (1-ethylphenyl-4,5-diphenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and N-benzylidene-2-phenylethylamine (36 mg, 172 μmol).
Orange solid: 90 mg (119 μmol, 69%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.55 (s, 15H), 1.76 (s, 1H), 2.33 (s, 3H), 2.89 (s, 1H), 3.91 (s, 1H), 4.55 (s, 1H), 6.89 (d, J = 6.8Hz, 2H), 7.11-7.16 (m, 5H), 7.32-7.35 (m, 5H), 7.44 (d, J = 6.7Hz, 2H), 7.59 -7.63 (m, 5H), 12.23 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 9.26 (q, 5C), 21.54 (q), 37.69 (t), 50.59 (t), 101.14 (s, d: J _{C, Rh} = 5.4 Hz , 5C), 126.53 (d), 126.83 (s), 126.85 (d, 2C), 128.33 (d), 128.74 (s), 128.78 (d, 2C), 128.92 (s), 129.50 (d, 3C), 129.62 (d, 2C), 130.05 (d, 3C), 130.46 (s), 131.59 (d, 2C), 132.73 (s), 138.56 (s), 140.63 (s), 166.66 (s, d: J _{c, Rh} = 54.6 Hz); IR (KBr disc): υ~ = 3058, 3027, 2916, 1634, 1600, 1491, 1452, 1400, 1377, 1174, 1110, 1086, 1028, 1010, 964, 812, 765, 703, 637, 575, 508 cm ^-1 ; HR-MS (ESI (+)): m / z = 753.1832, calcd. For C ₄₀ H ₄₃ ClN ₂ O ₂ RhS [M + H ⁺ ] ⁺ : 753.1783. 5. Dichloro (cp *) (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and 3,4-dihydroisoquinoline (23 mg, 172 μmol).
Orange solid: 102 mg (150 μmol, 87%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.61 (s, 15H), 2.26 (s, 3H), 3.14 (t, J = 5.8 Hz, 2H), 4.49-4.58 (m, 2H), 7.02 (d, J = 7.8 Hz, 2H), 7.12 (t, J = 7.6 Hz, 1H), 7.25 (t, J = 7.4 Hz, 1H), 7.33 (d, J = 7.6 Hz, 1H), 7.37 ( d, J = 7.8Hz, 1H), 7.49-7.51 (m, 7H), 11.26 (s, 1H) ppm; ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.48 (q, 5C), 21.48 (q), 30.39 (t), 45.61 (t), 101.04 (s, d: J _{C, Rh} = 5.6 Hz , 5C), 124.24 (d), 126.50 (s), 126.67 (d, 3C), 127.50 (d), 128.22 (d, 2C), 128.71 (d, 3C), 128.77 (s), 128.97 (d), 129.54 (s), 129.71 (s), 129.81 (d, 2C), 129.86 (s), 134.50 (s), 140.37 (s), 165.05 (s, d: J _{C, Rh} = 54.4 Hz); IR (KBr disc): υ~ = 3445, 3058, 2972, 2914, 1649, 1482, 1451, 1381, 1177, 1086, 1033, 813, 767, 727, 703, 681, 637, 575, 508 cm ^-1 ; HR-MS (ESI (+)): m / z = 675.1333, calc'd for C ₃₄ H ₃₇ ClN ₂ O ₂ RhS [M + H ^{+] +:.} 675.1314. 6. Dichloro (cp *) (1-cyclohexyl-4,5-diphenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and N-benzylidene-cyclohexylamine (32 mg, 172 μmol).
Orange solid: 82 mg (113 μmol, 66%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.16-1.53 (m, 8H), 1.64 (s, 15H), 2.31 (s, 3H), 4.83 (t, J = 12.1 Hz), 7.03 ( d, J = 7.9Hz, 2H), 7.18 (d, J = 6.9Hz, 2H), 7.25-7.38 (m, 7H), 7.47-7.56 (m, 3H), 12.09 (s, 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.45 (q, 5C), 21.49 (q), 25.74 (t), 26.93 (t), 33.37 (t), 35.23 (t), 62.94 (i.e. ), 101.14 (s, d: J _{C, Rh} = 5.4 Hz, 5C), 126.29 (d, 2C), 126.91 (d, 2C), 128.11 (d, 2C), 128.62 (s), 129.01 (s), 129.15 (d, 2C), 129.47 (d, 3C), 130.36 (d), 130.84 (s), 132.46 (s), 133.40 (d, 2C), 140.33 (s), 151.04 (s), 165.16 (s, d: J _{C, Rh} = 55.3 Hz); IR (KBr disc): υ~ = 3058, 2930, 2857, 1635, 1558, 1541, 1508, 1489, 1456, 1362, 1174, 1113, 1086, 1026, 1012, 996, 964, 894, 811, 790, 769 , 753, 707, 634, 600, 576, 509, 420 cm ^-1 ; m / z = 731.1940, calc'd for C ₃₈ H ₄₅ ClN ₂ O ₂ RhS [M + H ^{+] +:.} 731.1940. 7. Dichloro (cp *) (1- (2-methoxyethyl) -4,5-diphenyl-imidazol-2-ylidene) rhodium (III)

According to Method E, the indicated compound was synthesized from RhCl ₂ (cp *) (Ph-TosMIC) (100 mg, 172 μmol) and N-benzylidene-cyclohexylamine (28 mg, 172 μmol).
Orange solid: 85 mg (120 μmol, 70%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.58 (s, 15H), 2.31 (s, 3H), 2.94 (s, 3H), 2.99-3.03 (m, 1H), 3.21-3.28 (m , 1H), 4.08 (quin, J = 6.7 Hz, 1H), 4.34-4.43 (m, 1H), 7.08 (d, J = 8.0 Hz, 2H), 7.26-7.25 (m, 7H), 7.50-7.53 ( m, 5H), 11.97 (s, 1H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 9.25 (q, 5C), 21.50 (q), 47.58 (t), 58.69 (q), 72.25 (t), 101.20 (s, d: J _{C , Rh} = 5.5Hz, 5C), 126.52 (d, 3C), 126.92 (d, 2C), 128.26 (d, 2C), 128.72 (s), 128.88 (s), 129.43 (s), 129.56 (d, 2C ), 129.68 (d, 3C), 130.21 (s), 131.35 (s), 131.68 (d, 2C), 133.33 (s), 140.52 (s), 166.93 (s, d: J _{c, Rh} = 55.2 Hz) ppm; IR (KBr disc): υ~ = 3035, 2974, 2917, 1635, 1595, 1507, 1490, 1447, 1375, 1319, 1261, 1171, 1123, 1087, 1025, 1011, 963, 806, 769, 694, 633 , 595, 576, 537, 508, 473 cm ^-1 ; HR-MS (ESI (+)): m / z = 671.1832, calc'd for C ₃₅ H ₄₀ N ₂ O ₃ RhS [M-Cl ^{-] +:.} 671.1815.

III. Iridium chemistry

General Procedure F: Synthesis of Ir Isocyanide Complex

In a typical protocol, [IrCl ₂ (cp *)] ₂ and the isocyanide were dissolved in DCM and stirred at room temperature for 2 hours. Subsequently, the product was purified by recrystallization in DCM / Et ₂ O. 1. Dichloro (cp *) (Ph-TosMIC) iridium (III)

According to Method F, the indicated compound was synthesized from [IrCl ₂ (cp *)] ₂ (1.26 g, 1.59 mmol) and Ph-TosMIC (819 mg, 3.17 mmol).
Orange solid: 1.35 g (2.02 mmol, 64%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.84 (q, 15H), 2.43 (s, 3H), 6.10 (s, 1H), 7.26-7.30 (m, 3H), 7.32-7.38 (m , 3H), 7.41-7.47 (m, 1H), 7.54-7.59 (t, J = 8.40 Hz, 2H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 9.38 (q, 5C), 22.09 (q), 79.01 (d), 96.29 (s, 5C), 127.73 (s), 128.62 (d), 129.73 (d, 3C), 130.45 (s), 130.64 (s), 130.95 (d, 3C), 131.23 (d, 2C), 147.40 (s), _CN is missing; IR (KBr disc): υ~ = 3444, 2887, 2168, 1633, 1595, 1493, 1455, 1382, 1333, 1185, 1155, 1083, 1030, 818, 780, 723, 697, 670, 628, 574, 557 , 508, 480, 438 cm ^-1 ; HR-MS (ESI (+)): m / z = 671.1832, calc'd for C ₃₅ H ₄₀ N ₂ O ₃ IrS [M-Cl ^{-] +:.} 671.1815. 2. Dichloro (cp *) (p-MeO-C ₆ H ₄ -TosMIC) iridium (III)

According to Method F, the indicated compound was synthesized from [IrCl ₂ (cp *)] ₂ (100 mg, 126 μmol) and p-MeO-C ₆ H ₄ -TosMIC (76 mg, 252 μmol).
Yellow solid: 135 mg (193 μmol, 77%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.84 (s, 15H), 2.44 (s, 3H), 3.80 (s, 3H), 6.02 (s, 1H), 6.86 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.3 Hz, 2H), 7.58 (d, J = 8.3 Hz, 2H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.23 (q, 5C), 21. 69 (q), 55.83 (q), 78.54 (d) 96.04 (s, 5C), 114.62 (d, 2C ), 119.20 (s), 129.95 (d, 2C), 130.42 (s), 130.49 (d, 2C), 130.79 (d, 2C), 147.13 (s), 161.94 (s), C _CN not detectable; IR (KBr disc): υ ~ = 2981, 2919, 2164, 1604, 1595, 1513, 1451, 1381, 1335, 1309, 1290, 1257, 1179, 1154, 1083, 1029, 836, 814, 772, 709, 676 , 660, 620, 600, 566, 518, 473 cm ^-1 ; HR-MS (ESI (+)): m / z = 664.1271, calc'd for C ₂₆ H ₃₀ ClNO ₃ IrS [M-Cl ^{-] +:.} 664.1264. 3. Dichloro (cp *) (methyl isocyano (phenyl) acetate) iridium (III)

According to Method F, the indicated compound was synthesized from [IrCl ₂ (cp *)] ₂ (100 mg, 126 μmol) and methyl isocyano (phenyl) acetate (44 mg, 252 μmol).
Yellow solid: 136 mg (237 μmol, 94%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.80 (q, 15H), 3.80 (s, 3H), 5.80 (s, 1H), 7.42-7.55 (m, 5H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 9.15 (q, 5C), 54.36 (q), 63.01 (d), 95.09 (s, 5C) 127.18 (d, 2C), 129.78 (d, 2C ), 130.24 (d), 132.12 (s), 166.51 (s); IR (KBr disc): υ ~ = 2956, 2917, 2883, 2190, 1754, 1632, 1494, 1453, 1380, 1340, 1254, 1218, 1080, 1031, 981, 867, 791, 750, 701, 622, 559 , 488, 436 cm ^-1 ; HR-MS (ESI (+)): m / z = 664.1264, calc. for C ₂₆ H ₃₀ ClNO ₃ IrS [M-Cl ^- ] ⁺ : 671.1815. General Procedure G: Synthesis of Ir NHC Complexes

In a typical protocol, IrCl ₂ (cp *) (Ar-TosMIC) (173 μmol), imine (173 μmol) and NEt ₃ (100 μl / μmol [Ir]) were dissolved in 5 ml of MeCN. After stirring at room temperature for 12 hours, the solution was quenched with 20 mL of water, separated, and the water phase was extracted with DCM (3 × 10 mL). The combined organic phases were dried with MgSO ₄ and the solvent was removed under reduced pressure. The resulting solid was purified by recrystallization in DCM / Et ₂ O. 1. Dichloro (cp *) (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and N-benzylidene-2-propylamine (22 mg, 149 μmol).
Yellow solid: 64 mg (82 μmol, 55%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.17 (d, J = 6.7 Hz, 3H), 1.19 (d, J = 7.1 Hz, 3H), 1.64 (s, 15H), 2.34 (s, 3H), 5.18 (sept, J = 6.8 Hz, 1H), 7.07 (d, J = 7.8 Hz, 2H), 7.17 (d, J = 7.5 Hz, 2H), 7.22-7.29 (m, 3H), 7.33 ( d, J = 7.6 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.48-7.56 (m, 3H), 12.07 (s, 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 9.09 (q, 5C), 21.46 (q), 23.31 (q), 25.69 (q), 66.22 (d), 94.87 (s, 5C), 126.39 (d, 2C), 127.01 (d, 2C), 127.97 (d, 2C), 128.61 (s), 129.19 (d, 3C), 129.41 (d, 3C), 130.34 (s), 130.52 (s), 131.33 (s), 131.78 (s), 133.63 (d, 2C), 140.24 (s), 147.37 (s); IR (KBr disc): υ~ = 3443, 2977, 2918, 1631, 1557, 1539, 1490, 1459, 1381, 1285, 1178, 1090, 1032, 813, 770, 705, 641, 578, 513 cm ^-1 ; HR-MS (ESI (+)): m / z = 781.2211, calc'd for C ₃₅ H ₄₁ ClN ₂ O ₂ IrS [M + H ^{+] +:.} 781.2201. 2. Dichloro (cp *) (5- (4-bromophenyl) -1-isopropyl-4-phenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and Np-bromobenzylidene-2-propylamine (34 mg, 149 μmol).
Yellow solid: 56 mg (65 μmol, 44%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.14 (d, J = 6.7 Hz, 3H), 1.21 (d, J = 7.0 Hz, 3H), 1.63 (s, 15H), 2.33 (s, 3H), 5.21 (sept, J = 6.7 Hz, 1H), 7.07 (d, J = 7.9 Hz, 2H), 7.18 (d, J = 7.7 Hz, 2H), 7.26-7.32 (m, 5H), 7.35 ( d, J = 7.6 Hz, 2H), 7.66 (d, J = 8.3 Hz, 2H), 12.10 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 9.09 (q, 5C), 21.47 (q), 23.44 (q), 25.76 (q), 54.08 (d) 94.91 (s, 5C), 124.87 ( s), 126.53 (d, 2C), 127.00 (d, 2C), 127.98 (d, 2C), 128.70 (s), 128.84 (s), 129.55 (d, 2C), 129.89 (s), 132.14 (s) , 132.58 (d, 2C), 135.28 (d, 3C), 140.30 (s), 148.13 (s), 151.11 (s); IR (KBr disc): υ~ = 3442, 2977, 2917, 1631, 1601, 1503, 1486, 1458, 1366, 1349, 1298, 1234, 1172, 1124, 1088, 1075, 1034, 1011, 966, 913, 835 , 803, 770, 725, 694, 640, 579, 538, 514, 499, 478 cm ^-1 ; HR-MS (ESI (+)): m / z = 859.1319, calc'd for C ₃₅ H ₄₀ O ₂ S ₂ ClIrN ⁷⁹ Br [M + H ^{+] +:.} 859.1298. 3. Dichloro (cp *) (1-isopropyl-4- (4-methoxyphenyl) -5-phenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (p-MeOC ₆ H ₄ -TosMIC) (100 mg, 143 μmol) and N-benzylidene-2-propylamine (21 mg, 143 μmol).
Yellow solid: 14 mg (11 μmol, 8%); ¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.10 (d, J = 6.8 Hz, 3H), 1.17 (d, J = 6.8 Hz, 3H), 1.63 (s, 15H), 2.34 (s, 3H), 3.75 (s, 3H), 5.15 (sept, J = 6.8 Hz, 1H), 6.79 (d, J = 8.8 Hz, 2H), 7.07 (d, J = 8.3 Hz, 2H), 7.09 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 7.6 Hz, 2H), 7.41 (d, J = 7.6 Hz, 1H), 7.33 (d, J = 7.6 Hz, 1H), 7.46-7.55 (m, 3H), 11.95 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 8.91 (q, 5C), 21.29 (q), 23.11 (q), 25.49 (q), 53.73 (d), 55.63 (q), 94.62 (s , 5C), 114.59 (d, 2C), 121.29 (s), 126.79 (d, 2C), 127.63 (d, 2C), 127.77 (d, 2C), 128.96 (d, 2C), 130.02 (d), 130.05 (s), 130.54 (s), 131.54 (s), 133.56 (d, 2C), 140.02 (s), 146.37 (s), 150.95 (s), 159.84 (s). 4. Dichloro (cp *) (1-benzyl-4,5-diphenyl-imidazol-2-ylidene) iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and N-benzylidenebenzylamine (29 mg, 149 μmol).
Yellow solid: 96 mg (116 μmol, 78%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.66 (s, 15H), 2.42 (s, 3H), 4.70 (d, J = 14.4 Hz, 1H), 5.90 (d, J = 14.5 Hz, 1H), 6.34 (d, J = 7.6 Hz, 2H), 6.84 (q, J = 8.0 Hz, 4H), 7.01 (t, J = 7.4 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H) , 7.21 (t, J = 7.7Hz, 2H), 7.26-7.34 (m, 6H), 7.51 (d, J = 8.0Hz, 2H), 12.47 (s, 1H) ppm; ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 9.04 (q, 5C), 21.59 (q), 51.97 (t), 95.07 (s, 5C), 126.25 (d, 3C), 127.38 (d) , 127.74 (d, 2C), 127.96 (d, 2C), 128.10 (d, 2C), 128.29 (d, 2C), 128.82 (d), 129.19 (d, 2C), 129.25 (s), 129.53 (d, 2C), 129.66 (s), 130.81 (s), 131.42 (d, 2C), 132.36 (s), 137.66 (s), 140.43 (s), 148.29 (s), 150.83 (s); IR (KBr disc): υ~ = 3439, 3059, 2917, 1635, 1559, 1540, 1507, 1490, 1456, 1378, 1354, 1171, 1089, 1028, 1011, 976, 956, 808, 760, 731, 696 , 640, 578, 514, 419 cm ^-1 ; HR-MS (ESI (+)): m / z = 673.1983, calc'd for C ₃₂ H ₃₃ ClIrN ₂ [M-Ts ^{-] +:.} 673.1962. 5. Dichloro (cp *) (1-ethylphenyl-4,5-diphenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and N-benzylidenes-2-phenylethylamine (31 mg, 149 μmol).
Yellow solid: 80 mg (95 μmol, 64%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 1.55 (s, 15H), 2.35 (s, 3H), 2.92 (s, 1H), 3.89 (s, 1H), 4.46 (s, 1H), 6.86 (d, J = 6.7Hz, 2H), 7.11-7.15 (m, 5H), 7.30-7.33 (m, 5H), 7.46 (d, J = 5.9Hz, 2H), 7.56-7.62 (m, 5H) , 12.33 (s, 1H); ¹³ C NMR (100 MHz, CD ₂ Cl ₂ ): δ = 8.90 (q, 5C), 21.52 (q), 50.34 (t), 94.87 (s, 5C), 126.65 (d, 2C), 126.80 (d) , 126.82 (d), 128.17 (d, 2C), 128.76 (s), 128.78 (d, 3C), 128.86 (s), 129.50 (d, 3C), 129.54 (d, 2C), 129.63 (s), 130.03 (d, 3C), 130.40 (s), 130.70 (s), 131.63 (d, 2C), 139.00 (s), 140.48 (s), 148.54 (s); IR (KBr disc): υ~ = 3059, 3025, 2957, 2917, 1633, 1600, 1490, 1451, 1397, 1377, 1358, 1315, 1171, 1108, 1089, 1030, 1010, 963, 924, 844, 806 , 767, 738, 699, 642, 599, 578, 513 cm ^-1 ; HR-MS (ESI (+)): m / z = 843.2377, calcd. For C ₄₀ H ₄₃ IrN ₂ O ₂ S ³⁵ Cl [M + H ⁺ ] ⁺ : 843.2358. 6. Dichloro (cp *) (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidene) iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and 3,4-dihydroisoquinoline (20 mg, 149 μmol).
Green solid: 64 mg (84 μmol, 56%); ¹ H NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.64 (s, 15H), 2.29 (s, 3H), 3.11-3.15 (m, 2H), 4.44-4.53 (m, 2H), 7.05 (i.e. , J = 7.9 Hz, 2H), 7.12 (t, J = 7.6, 1H), 7.24 (t, J = 7.4 Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1H), 7.45-7.52 (m, 7H), 11.18 (s, 1H); ¹³ C NMR (150 MHz, CD ₂ Cl ₂ ): δ = 9.17 (q, 5C), 21.45 (q), 30.48 (t), 45.39 (t), 94.80 (s, 5C), 124.33 (d), 126.45 (s), 126.58 (s), 126.76 (d, 3C), 127.46 (d), 128.04 (d, 2C), 128.76 (d), 128.81 (d, 2C), 128.95 (d), 129.74 (s), 129.78 (d, 2C), 129.84 (s), 134.69 (s), 140.20 (s), 146.97 (s), 151.39 (s); IR (KBr disc): υ~ = 3060, 2962, 2917, 1635, 1482, 1452, 1380, 1341, 1175, 1091, 1037, 1015, 924, 813, 766, 726, 701, 641, 578, 513, 438 cm ^-1 ; HR-MS (ESI (+)): m / z = 765.1907, calc. For C ₃₄ H ₃₇ IrN ₂ O ₂ S ³⁵ Cl [M + H ⁺ ] ⁺ : 765.1888. 7. Dichloro (cp *) (1-cyclohexyl-4,5-diphenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and N-benzylidene-cyclohexylamine (28 mg, 149 μmol).
Yellow solid: 65 mg (79 μmol, 53%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.11-1.48 (m, 8H), 1.65 (s, 15H), 1.72-1.74 (m, 2H), 2.12 (s, 1H), 2.34 (s , 3H), 4.71 (s, 1H), 7.05 (s, 1H), 7.07 (s, 1H), 7.15-716 (m, 1H), 7.17-7.18 (m, 1H), 7.23-7.30 (m, 5H ), 7.39 (d, J = 1.65 Hz, 1H), 7.42 (d, J = 1.26 Hz, 1H), 7.48-7.50 (m, 1H), 7.52-7.58 (m, 2H), 12.22 (s, 1H) ; IR (KBr disc): υ~ = 3443, 3057, 2929, 2857, 1631, 1598, 1489, 1458, 1362, 1263, 1177, 1112, 1088, 1030, 965, 898, 792, 770, 703, 640, 578 , 514, 481, 421 cm ^-1 ; HR-MS (ESI (+)): m / z = 843.2341, calcd. For C ₃₈ H ₄₄ ClIrN ₂ NaO ₂ S [M + Na ⁺ ] ⁺ : 843.2326. 8. Dichloro (cp *) (1- (2-methoxyethyl) -4,5-diphenyl-imidazol-2-ylidene) -iridium (III)

According to Method G, the indicated compound was synthesized from IrCl ₂ (cp *) (Ph-TosMIC) (100 mg, 149 μmol) and N-benzylidene-2-hydroxyethylamine (25 mg, 149 μmol).
Yellow solid: 92 mg (116 μmol, 78%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.59 (s, 15H), 2.34 (s, 3H), 2.96 (s, 3H), 3.05-3.12 (m, 1H), 3.24-3.31 (m , 1H), 4.01-4.10 (m, 1H), 4.33-4.42 (m, 1H), 7.11 (d, J = 8.0 Hz, 2H), 7.22-7.38 (m, 7H), 7.47-7.55 (m, 5H ), 12.03 (s, 1H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): δ = 8.89 (q, 5C), 21.48 (q), 47.29 (t), 58.74 (q), 72.33 (t), 94.94 (s, 5C), 126.65 (d, 2C), 126.88 (d, 2C), 128.12 (d, 2C), 128.73 (s), 128.83 (s), 129.48 (d, 3C), 129.70 (d, 3C), 130.19 (s), 130.51 (s), 131.67 (d, 2C), 132.08 (s), 140.42 (s), 148.80 (s), 151.05 (s); IR (KBr disc): υ~ = 3058, 2976, 2919, 1632, 1596, 1490, 1460, 1377, 1316, 1173, 1121, 1090, 1030, 1011, 964, 808, 768, 700, 640, 598, 578 , 513, 477 cm ^-1 ; HR-MS (ESI (+)): m / z = 819.2002, calc'd for C ₃₅ H ₄₀ NaO ₃ S ₂ ClIrN [M + Na ^{+] +:.} 819.1975.

IV. Ruthenium chemistry

General Procedure H: Synthesis of Ru Isocyanide Complexes

In a typical protocol, [RuCl ₂ (η ⁶ -p-cymene)] ₂ and the isocyanide were dissolved in DCM and stirred at room temperature for 14 hours. Then the solvent was removed under reduced pressure. The resulting solid was the analytically pure isocyanide complex. 1. Dichloro (η ⁵ -p-cymene) (Ph-TosMIC) ruthenium (II)

According to Method H, the indicated compound was synthesized from [RuCl ₂ (η ⁶ -p-cymene)] ₂ (200 mg, 327 μmol) and Ph-TosMIC (177 mg, 654 μmol).
Orange solid: 377 mg (654 μmol, quantitative); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.28 (d, J = 6.9 Hz, 3H), 1.28 (d, J = 6.9 Hz, 3H), 2.28 (s, 3H), 2.42 (s, 3H), 2.88 (sept, J = 6.9 Hz, 1H), 5.55 (d, J = 6.4 Hz, 2H), 5.73 (d, 2H, J = 6.4 Hz), 6.08 (s, 1H), 7.25-7.37 ( m, 6H), 7.38-7.46 (m, 1H), 7.54-7.60 (m, 2H); ¹³ C NMR (75 MHz, CD ₂ Cl ₂ ): = 19.01 (q), 21.95 (q), 22.53 (q), 22.57 (q), 31.63 (d), 89.84 (d, 2C), 89.94 (d, 2C), 90.02 (d), 109.02 (s), 109.81 (s), 128.59 (d, 2C), 129.19 (d, 2C), 130.42 (d, 2C), 130.82 (d, 2C), 131.06 (s) , 147.25 (s), 156.94 (s); IR (KBr disc): υ~ = 3450, 3063, 2964, 2921, 2871, 2166, 1628, 1596, 1494, 1456, 1332, 1307, 1294, 1177, 1155, 1084, 698, 671, 575, 509 cm ^{- 1} ; HR-MS (ESI (+)): m / z = 542.0492, calcd for C ₂₅ H ₂₇ ClNO ₂ RuS [M-Cl ^- ] ⁺ : 542.0495. 2. Dichloro (η ⁶ -p-cymene) (p-MeO-C ₆ H ₄ -TosMIC) ruthenium (II)

According to Method H, the indicated compound was synthesized from [RuCl ₂ (η ⁶ -p-cymene)] ₂ (100 mg, 163 μmol) and Ph-TosMIC (98 mg, 326 μmol).
Orange solid: 198 mg (326 μmol, quantitative); ¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.27 (d, J = 6.9, 6H), 2.27 (s, 3H), 2.43 (s, 3H), 2.86 (sept, J = 6.9 Hz, 1H ), 3.79 (s, 3H) 5.55 (d, J = 5.4 Hz, 2H), 5.72 (d, J = 5.4 Hz, 2H), 6.03 (s, 1H), 6.84 (d, J = 8.5 Hz, 2H) , 7.20 (d, J = 8.5 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.0 Hz, 2H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.98 (q), 21.93 (q), 22.48 (q), 22.53 (q), 31.57 (d), 55.79 (q), 78.53 (d), 89.74 (d), 89.83 (d), 89.85 (d), 89.86 (d), 108.91 (s), 109.58 (s), 114.52 (d, 2C), 119.15 (s), 130.05 (d, 2C), 130.38 (d, 2C), 130.49 (s), 130.78 (d, 2C), 147.10 (s), 152.72 (s), 161.86 (s); IR (KBr disc): υ ~ = 3039, 2962, 2930, 2901, 2167, 1608, 1596, 1540, 1513, 1457, 1389, 1331, 1309, 1291, 1253, 1180, 1153, 1085, 1057, 1033, 838 , 811, 765, 712, 660, 635, 602, 568, 519, 454 cm ^-1 ; HR-MS (ESI (+)): m / z = 630.0185, calc'd for C ₂₆ H ₂₉ Cl ₂ NO ₃ Rušná [M + Na ^{+ -] +.} 630.0186. 3. Dichloro (η ⁶ -p-cymene) (methyl isocyano (phenyl) acetate) ruthenium (II)

According to Method H, the indicated compound was synthesized from [RuCl ₂ (η ⁶ -p-cymene)] ₂ (100 mg, 163 μmol) and methyl isocyano (phenyl) acetate (57 mg, 326 μmol).
Orange solid: 157 mg (326 μmol, quantitative); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.25 (d, J = 6.9, 6H,), 2.24 (s, 3H), 2.85 (sept, J = 6.9 Hz, 1H), 3.79 (s, 3H) 5.44 (d, J = 6.0 Hz, 1H), 5.50 (d, J = 6.0 Hz, 1H), 5.65 (d, J = 6.0 Hz, 1H), 5.67 (d, J = 6.0 Hz, 2H,) , 5.83 (s, 1H), 7.40-7.46 (m, 3H), 7.48-7.54 (m, 2H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.87 (q), 22.45 (q), 22.48 (q), 31.51 (d), 62.96 (q), 80.77 (d), 81.49 (s), 88.28 (d), 88.63 (d), 89.23 (d), 89.49 (d), 108.59 (s), 108.63 (s), 127.14 (d, 2C), 129.61 (d, 2C), 130.08 (d), 131.94 (s), 166.61 (s); IR (KBr disc): υ~ = 3051, 2960, 2188, 1753, 1633, 1495, 1455, 1384, 1255, 1216, 1168, 1035, 866, 735, 698, 517 cm ^-1 ; HR-MS (FAB (+)): m / z = 446.0450, calcd. For C ₂₀ H ₂₃ ClNO ₂ Ru [M-Cl ^- ] ⁺ : 446.0461. 4. Dichloro (η ⁶ -p-cymene) (diphenylmethyl isocyano) ruthenium (II)

According to Method H, the indicated compound was synthesized from [RuCl ₂ (η ⁶ -p-cymene)] ₂ (159 mg, 259 μmol) and diphenylmethyl isocyanide (100 mg, 517 μmol).
Orange solid: 259 mg (517 μmol, quantitative); ¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.67 (d, J = 7.0 Hz, 6C), 2.21 (s, 3H), 2.67 (sept, J = 7.0 Hz, 1H), 5.41 (d, J = 6.1 Hz, 2H), 5.56 (d, J = 6.1 Hz, 2H), 6.31 (s, 1H), 7.33-7.47 (m, 9H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.88 (q), 22.48 (q, 2C), 31.64 (d), 64.84 (d), 88.34 (d, 2C), 88.43 (d, 2C) , 107.77 (s), 108.37 (s), 126.93 (d, 2C), 129.11 (s), 129.51 (d, 2C), 137.89 (s); IR (KBr disc): υ~ = 3059, 2965, 2186, 1631, 1540, 1494, 1455, 1382, 1031, 861, 804, 745, 702, 653, 611, 560, 451 cm ^-1 ; HR-MS (ESI (+)): m / z = 464.0749, calc'd for C ₂₄ H ₂₅ ClNRu [M-Cl ^{-] +:.} 464.0719. General Procedure I: Synthesis of Ru NHC Complexes

In a typical protocol, RuCl ₂ (η ⁶ -p-cymene) (Ar-TosMIC) (173 μmol), the imine (173 μmol), and NEt ₃ (100 μl / μmol [Ru]) were dissolved in 5 ml of DCM. After stirring at room temperature for 12 hours, the solution was quenched with 20 mL of water, separated, and the water phase was extracted with DCM (3 × 10 mL). The combined organic phases were dried with MgSO ₄ and the solvent was removed under reduced pressure. The resulting solid was purified by recrystallization in DCM / Et ₂ O. 1. Dichloro (η ⁶ -p-cymene) (1-isopropyl-4,5-diphenyl-imidazol-2-ylidene) ruthenium (II)

According to Method I, the indicated compound was synthesized from RuCl ₂ (η ⁶ -p-cymene) (Ph-TosMIC) (894 mg, 1.51 mmol) and N-benzylidenes-2-propylamine (222 mg, 1.51 mmol).
Yellow solid: 950 mg (1.38 mmol, 91%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.11 (d, J = 6.8 Hz, 3H), 1.24 (d, J = 6.8 Hz, 3H), 1.26 (d, J = 7.1 Hz, 3H) , 1.34 (d, J = 7.1 Hz, 3H), 2.07 (s, 3H), 2.36 (s, 3H) 2.70 (sept, J = 6.9 Hz, 1H), 5.26 (d, J = 6.1 Hz, 1H), 5.38 (d, J = 6.1 Hz, 1H), 5.44 (sept, J = 7.1 Hz, 1H), 5.45 (d, J = 6.1 Hz, 1H), 7.11-7.17 (m, 4H), 7.45 (d, J = 7.45 Hz, 2H), 7.48-7.56 (m, 5H), 12.97 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 17.8 (q), 20.5 (q), 20.6 (q), 22.5 (q), 22.9 (q), 23.5 (q), 30.2 (d), 88.0 (d), 89.7 (d, 2C), 91.3 (d), 94.1 (d, 2C), 125.4 (s), 125.5 (d, 2C), 125.8 (d), 127.4 (d), 127.5 (d) , 128.3 (d, 2C), 128.4 (d), 128.5 (d), 129.3 (d), 130.0 (d), 130.7 (d), 130.8 (d), 132.8 (s), 139.3 (d); IR (KBr disc): υ~ = 3427, 2966, 2930, 1626, 1595, 1490, 1469, 1444, 1368, 1345, 1261, 1152, 1089, 1025, 1009, 806, 782, 702, 639, 577 cm ^{- 1} ; HR-MS (ESI (+)): m / z = 689.1547, calc'd for C ₃₅ H ₄₀ ClN ₂ O ₂ RuS [M + H ^{+] +:.} 689.1542. 2. Dichloro (η ⁶ -p-cymene) (1-cyclohexyl-4,5-diphenyl-imidazol-2-ylidene) ruthenium (II)

According to Method I, the indicated compound was synthesized from RuCl ₂ (η ⁶ -p-cymene) (Ph-TosMIC) (100 mg, 173 μmol) and N-benzylidenecyclohexylamine (33 mg, 173 μmol).
Beige solid: 82 mg (113 μmol, 65%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 0.73 (qt, J = 13.0, 3.5 Hz, 1H), 1.12 (d, J = 6.9 Hz, 3H), 1.26 (d, J = 6.9 Hz, 3H), 1.26-1.38 (m, 1H), 1.42-1.79 (m, 6H), 1.89 (d, J = 11.3Hz, 1H), 2.09 (s, 3H), 2.35 (s, 3H), 3.72 (sept , J = 6.9 Hz, 1H), 5.01 (tt, J = 12.1, 3.0 Hz, 1H), 5.26 (d, J = 6.3 Hz, 1H), 5.35 (d, J = 6.3 Hz, 1H), 5.45 (i.e. , J = 6.3 Hz, 2H), 7.08-7.16 (m, 4H), 7.19-7.27 (m, 3H), 7.41 (d, J = 8.2 Hz, 2H), 7.44-7.60 (m, 6H), 13.04 ( s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 17.9 (t), 20.6 (q, 2C), 22.6 (q), 25.0 (q), 25.5 (t), 26.5 (t), 30.2 (t ), 33.4 (d), 34.3 (d), 62.4 (d), 88.4 (d), 89.6 (d), 91.2 (d), 94.1 (d), 102.3 (d), 109.8 (d), 125.4 (i.e. ), 125.5 (d, 2C), 127.4 (d), 127.5 (d, 2C), 128.2 (d), 128.4 (d, 3C), 129.3 (d), 130.2 (d), 130.7 (d), 131.0 ( d), 132.8 (d), 139.3 (d), 151.3 (d), 167.8 (d); IR (KBr disc): υ~ = 3425, 3057, 2931, 2856, 1967, 1628, 1595, 1540, 1507, 1490, 1468, 1456, 1444, 1362, 1331, 1208, 1154, 1113, 1088, 1025, 1010 , 994,962,924,895,847,807,789,768,752,705,669,639,603,576,528,419 cm ^-1 ; HR-MS (ESI (+)): m / z = 729.1888, calc'd for C ₃₈ H ₄₄ ClN ₂ O ₂ RuS [M + H ^{+] +:.} 729.1888. 3. Dichloro (η 6 -p-cymene) (1-phenylethyl-4,5-diphenyl-imidazol-2-ylidene) ruthenium (II)

According to Method I, the indicated compound was synthesized from RuCl ₂ (η ⁶ -p-cymene) (Ph-TosMIC) (100 mg, 173 μmol) and N-benzylidenes-2-phenylethylamine (37 mg, 173 μmol).
Green solid: 45 mg (60 μmol, 35%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.00 (d, J = 6.9 Hz, 3H), 1.12 (d, J = 6.9 Hz, 3H), 1.95 (s, 3H), 2.25 (s, 3H), 2.37 (td, J = 12.2, 5.0 Hz, 1H), 2.58 (sept, J = 6.9 Hz, 1H), 2.73-2.85 (m, 1H), 4.17 (td, J = 12.2, 5.0 Hz, 1H ), 4.53 (td, J = 12.2, 5.0 Hz, 1H), 5.11 (d, J = 6.1 Hz, 1H), 5.21-5.23 (m, 1H, solvent overlay), 5.29 (d, J = 6.1 Hz, 1H ), 5.30 (d, J = 6.1 Hz, 1H), 6.79 (d, J = 7.4 Hz, 2H), 7.01-7.15 (m, 6H), 7.19-7.29 (m, 5H), 7.41 (d, J = 7.9Hz, 2H), 7.43-7.48 (m, 3H), 7.52-7.55 (m, 2H), 12.83 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 17.8 (q), 20.6 (q), 30.2 (d), 36.7 (t, 2C), 50.2 (t, 2C), 88.4 (d,), 89.6 (d), 91.7 (d), 93.7 (s), 102.8 (s), 110.7 (d), 125.6 (s), 125.7 (d), 126.1 (d), 127.5 (d, 2C), 127.7 (i.e. ), 128.1 (s, 2C), 128.1 (d, 2C), 128.4 (d, 2C), 128.6 (d, 2C), 129.1 (d, 2C), 129.3 (d), 129.9 (d), 130.6 (i.e. , 2C), 131.1 (d); IR (KBr disc): υ ~ = 3058, 3027, 2963, 1955, 1634, 1599, 1542, 1491, 1454, 1391, 1360, 1155, 1089, 1031, 1009, 963, 847, 812, 766, 700, 639, 577, 511, 419 cm ^-1 ; HR-MS (ESI (+)): m / z = 773.1549 calc. For C ₄₀ H ₄₁ ClN ₂ O ₂ RuSNa [M + Na ⁺ ] ⁺ : 773.1520. 4. Dichloro (η ⁶ -p-cymene) (1-phenyl-5,6-dihydroimidazo [5,1-a] isoquinolin-3-ylidene) ruthenium (II)

According to Method I, the indicated compound was synthesized from RuCl ₂ (η ⁶ -p-cymene) (Ph-TosMIC) (100 mg, 173 μmol) and 3,4-dihydroisoquinoline (23 mg, 173 μmol).
Orange-brown solid: 88 mg (131 μmol, 76%); ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ 1.11 (d, J = 6.8 Hz, 3H), 1.23 (d, J = 6.8 Hz, 3H), 2.15 (s, 3H), 2.28 (s, 3H ), 2.64 (sept, J = 6.8 Hz, 1H), 3.10-3.19 (m, 2H), 4.24-4.36 (m, 1H), 4.71-4.83 (m, 1H), 5.42 (m, 1H, solvent overlay) , 5.42 (dd, J = 6.2, 1.0 Hz, 1H), 5.47 (dd, J = 6.2, 1.0 Hz, 1H), 5.51 (dd, J = 6.2, 1.0 Hz, 1H), 7.04 (d, J = 7.04 Hz, 2H), 7.12 (td, J = 7.5, 1.2 Hz, 1H), 7.24 (td, J = 7.5, 1.2 Hz, 1H), 7.30-7.39 (m, 3H), 7.42 (d, J = 7.42 Hz , 1H), 7.44-7.58 (m, 5H) 12.25 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.0 (q), 20.6 (q), 21.1 (q), 22.0 (q), 23.5 (d), 30.0 (t), 30.4 (d), 45.0 (d), 87.7 (d), 89.9 (d), 92.6 (d), 93.0 (d), 104.0 (d), 109.7 (d), 123.2 (d), 125.7 (d, 2C), 125.9 (i.e. ), 126.5 (d), 127.1 (d), 127.3 (d, 2C), 127.7 (d, 2C), 127.9 (d), 128.0 (d), 128.8 (d), 128.9 (d, 2C), 129.1 ( d), 133.6 (d), 139.1 (d), 150.6 (d), 167.3 (d); IR (KBr disc): υ~ = 3439, 3060, 2963, 2873, 2121, 1636, 1598, 1576, 1559, 1540, 1502, 1481, 1451, 1388, 1341, 1273, 1155, 1129, 1104, 1088, 1034 , 1009, 967, 924, 855, 811, 764, 749, 726, 699, 639, 601, 577, 511, 477, 419 cm ^-1 ; HR-MS (ESI (+)): m / z = 673.1248, calc. For C ₃₄ H ₃₆ ClN ₂ O ₂ RuS [M + H ⁺ ] ⁺ : 673.1248. 5. Dichloro (η ⁶ -p-cymene) (5- (4-bromophenyl) -1-isopropyl-4-phenyl-imidazol-2-ylidene) ruthenium (II)

According to Method I, the indicated compound was synthesized from RuCl ₂ (η ⁶ -p-cymene) (Ph-TosMIC) (100 mg, 173 μmol) and Np-bromobenzylidene-2-propylamine (39 mg, 173 μmol).
Beige solid: 55 mg (71 μmol, 42%); ¹ H NMR (400 MHz, CD ₂ Cl ₂ ): δ = 0.98 (d, J = 6.8 Hz, 3H), 1.13 (d, J = 6.8 Hz, 3H), 1.15 (d, J = 7.0 Hz, 3H) , 1.24 (d, J = 7.4 Hz, 3H) 1.95 (s, 3H), 2.25 (s, 3H), 2.69 (sept, J = 2.58, 1H), 5.13 (d, J = 6.2 Hz, 1H), 5.22 (d, J = 5.0 Hz, 1H), 5.26 (d, J = 6.2 Hz, 1H), 5.30-5.40 (m, 2H, solvent overlay), 7.00-7.07 (m, 4H), 7.12-7.20 (m, 3H), 7.27 (d, J = 8.2Hz, 2H), 7.35 (d, J = 8.0Hz, 2H), 7.55 (d, J = 8.2Hz, 2H), 12.91 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ 17.8 (q), 20.5 (q), 20.6 (q), 22.9 (q), 23.5 (q), 24.0 (q), 30.2 (d), 87.9 (d), 89.8 (d, 2C), 91.2 (d, 2C), 94.2 (d), 123.8 (d), 125.5 (d, 2C), 125.8 (d, 2C), 127.5 (d, 2C), 127.7 (d), 128.0 (d), 128.5 (d), 128.6 (d), 129.0 (d), 129.3 (d), 131.2 (d, 2C), 131.6 (d), 134.4 (d, 2C); IR (KBr disc): ν = IR (KBr disc): = 3439, 3057, 2967, 2932, 2873, 1967, 1628, 1601, 1506, 1487, 1469, 1390, 1367, 1345, 1297, 1232, 1153, 1122, 1088, 1075, 1032, 1010, 963, 835, 806, 769, 728, 695, 639, 576, 513, 477, 418 cm ^-1 ; HR-MS (ESI (+)): m / z = 767.0652, calc'd for C ₃₅ H ₃₉ BrClN ₂ O ₂ RuS [M + H ^{+] +:.} 767.0652. 6. Dichloro (η ⁶ -p-cymene) (1-isopropyl-4- (4-methoxyphenyl) -5-phenyl-imidazol-2-ylidene) ruthenium (II)

According to Method I, the indicated compound was prepared from RuCl ₂ (η ⁶ -p-cymene) (MeO-C ₆ H ₄ -TosMIC) (100 mg, 165 μmol) and N-benzylidene-2-propylamine (24 mg, 165 μmol ).
Beige solid: 64 mg (89 μmol, 54%); ¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.10 (d, J = 6.9 Hz, 3H), 1.24 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.9 Hz, 3H) , 1.33 (d, J = 7.2 Hz, 3H), 2.06 (s, 3H), 2.36 (s, 3H), 2.60 (sept, J = 6.9, 1H), 3.73 (s, 3H), 5.24 (d, J = 6.0 Hz, 1H), 5.36 (d, J = 6.0 Hz, 1H), 5.41 (sept, J = 7.2 Hz, 1H), 5.44 (d, J = 6.0 Hz, 1H), 6.77 (d, J = 8.7 Hz, 2H), 7.07 (d, J = 8.7 Hz, 2H), 7.14 (d, J = 7.9 Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H), 7.48-7.54 (m, 4H), 12.84 (s, 1H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.49 (q), 21.17 (q), 21.37 (q), 23.21 (q), 23.56 (q), 24.64 (q), 30.86 (d), 54.33 (d), 55.58 (q), 88.53 (d), 90.34 (d), 91.96 (d), 94.80 (d), 102.82 (s), 110.51 (s), 114.52 (d, 2C), 121.57 (s 126.16 (d, 2C), 126.53 (s), 127.52 (d, 2C), 128.21 (d, 2C), 128.92 (d), 129.20 (d), 129.93 (d), 130.37 (s), 130.86 ( s), 131.48 (s), 133.56 (d), 139.99 (s), 152.20 (s), 159.63 (s), 167.16 (s); IR (KBr disc): υ ~ = IR (KBr disc): = 2966, 1611, 1517, 1495, 1465, 1346, 1300, 1251, 1180, 1152, 1088, 1029, 961, 835, 776, 708, 638, 577, 513 cm ^-1 ; HR-MS (ESI (+)): m / z = 741.1486, calc'd for C ₃₆ H ₄₁ ClN ₂ O ₃ Rušná [M + Na ^{+] +:.} 741.1471

Claims (13)

A process for the preparation of metal-N-heterocyclic carbene complexes (metal-NHC complexes) by modular three-component template synthesis, comprising reacting a metal ligand compound ML _m L ' _n with the formula (II), a CH-acidic isocyanide with the general Formula (III) and an imine having the general formula (IV).

wherein M is selected from Au, Rh, Ir or Ru, L and L 'are a ligand suitable for the respective metal, which by coordination also gives m and n, the number of ligands, where m and n are each 0, 1 , 2, 3 or 4, Ar is selected from an unsubstituted, monosubstituted or disubstituted phenyl group, the substituents independently of one another selected from the group consisting of a hydrogen atom, a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical , a (C ₁ -C ₁₅ ) thioalkyl radical, a (C ₃ -C ₁₅ ) cycloalkyl radical, the one or may have a plurality of heteroatoms, a (C ₁ -C ₁₅ ) alkoxy, a trifluoromethyl group, bromine, chlorine and fluorine are selected, Ar 'from a straight-chain or branched-chain (C ₁ -C ₁₅ ) alkyl radical or from a non-, mono is selected from the group consisting of a hydrogen atom, a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical, a (C ₁ -C ₁₅ ) -thioalkyl radical, a (C C ₃ -C ₁₅ ) -cycloalkyl radical which may have one or more heteroatoms, a (C ₁ -C ₁₅ ) -alkoxy radical, a trifluoromethyl group, bromine, chlorine and fluorine, R is selected from a straight-chain or branched-chain, unsubstituted or substituted (C C ₁ -C ₁₅ ) -alkyl radical, where the substituents may be terminal phenyl radicals and the alkyl radicals may be linked by ether compounds, a (C ₃ -C ₁₅ ) -cycloalkyl radical containing one or more heteroatoms, such as O, or S, may be selected from an unsubstituted, monosubstituted, or disubstituted phenyl or benzyl group, the substituents being selected independently of one another from the group α, or R being an alkylene linker to which terminally a group according to formula (II) I), or R is an alkylene linker terminally attached to a phosphine moiety which may optionally be metal coordinated, or Ar 'and R together ring-seal a 3,4-dihydroisoquinoline moiety, and EWG for is an electron-withdrawing group, whereby metal-imidazol-2-ylidene complexes according to the general formula (I) are obtained. Process according to claim 1, wherein the metal ligand starting compound (II) consists of (THT) AuCl, (DMS) AuCl, (RhCl ₂ (cp *)) - dimer, (IrCl ₂ (cp *)) - dimer, [RuCl ₂ ( cymene)] - dimer, [RuCl ₂ (benzene)] - dimer or [RuCl ₂ (toluene)] - dimer is selected. The method of claim 1, wherein M is Au. A process according to any one of claims 1 to 3, wherein M is Au and the synthesis is carried out in a one-pot reaction. A process according to any one of claims 1 to 3, wherein when M is Rh or Ir, first the compounds (II) and (III) are reacted and then the generated rhodium or iridium isocyanide complexes with the imine (IV) with the addition of an amine base, preferably triethylamine. A process according to any one of claims 1 to 5, wherein the solvent is acetone, acetonitrile, benzene, toluene, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethane, diethyl ether, diethylene glycol dimethyl ester, DM (1,2-dimethoxyethane), dimethylformamide, Dimethyl sulfoxide, dioxane, ethyl acetate, hexamethyl phosphoramide, hexamethyl phosphoric triamide, pentane, hexane, cyclohexane, methyl tert-butyl ether, N-methyl-2-pyrrolidinone, nitromethane, petroleum ether, tetrahydrofuran, toluene or xylenes. Metal-N-heterocyclic carbene complexes (metal NHC complexes) according to the general formula (I):

wherein M is selected from Au, Rh, Ir or Ru, L and L 'are a ligand suitable for the respective metal, which by coordination also gives m and n, the number of ligands, where m and n are each 0, 1 , 2, 3 or 4, Ar is selected from an unsubstituted, monosubstituted or disubstituted phenyl group, the substituents independently of one another selected from the group consisting of a hydrogen atom, a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical one (C ₁ -C ₁₅ ) -thioalkyl radical, a (C ₃ -C ₁₅ ) -cycloalkyl radical which may have one or more heteroatoms, a (C ₁ -C ₁₅ ) -alkoxy radical, a trifluoromethyl group, bromine, chlorine and fluorine, Ar 'is selected from a straight-chain or branched-chain (C ₁ -C ₁₅ ) -alkyl radical or from an unsubstituted, monosubstituted or disubstituted phenyl group, where the substituents independently of one another are selected from the group consisting of a hydrogen atom, a straight-chain or branched-chain ( C ₁ -C ₁₅ ) -alkyl radical, a (C ₁ -C ₁₅ ) -thioalkyl radical, a (C ₃ -C ₁₅ ) -cycloalkyl radical which may have one or more heteroatoms, a (C ₁ -C ₁₅ ) -alkoxy radical, R is selected from a straight-chain or branched-chain, unsubstituted or substituted (C ₁ -C ₁₅ ) -alkyl radical, where the substituents may be terminal phenyl radicals and the alkyl radicals may be linked by ether compounds, a (C ₃ -C ₁₅ ) -Cycl oalkyl radical which may have one or more heteroatoms, such as O or S, an unsubstituted, mono- or disubstituted phenyl or benzyl group is selected, wherein the substituents are independently selected from the group α, or R is an alkylene linker in which in turn terminally hangs a group according to formula (I), or R stands for an alkylene linker at the terminal of which there is a phosphane unit which may optionally be metal-coordinated, or Ar 'and R together ring-closed for a 3, 4-dihydroisoquinoline unit. Metal-N-heterocyclic carbene complexes (metal NHC complexes) according to claim 7, which have the following structures:

Metal-N-heterocyclic carbene complexes (metal NHC complexes) according to claim 7, which have the following structures, wherein M is Rh or Ir:

Metal-N-heterocyclic carbene complexes (metal NHC complexes) according to claim 7, which have the following structures:

A process according to any of the preceding claims 1 to 6, wherein gold imidazol-2-ylidene complexes according to the general formula (I) are reacted with base, preferably triethylamine, to give gold-NHC trimers. Process according to claim 11, wherein the following gold NHC trimers are prepared:

Use of the metal-N-heterocyclic carbene complexes (metal-NHC complexes) according to any one of claims 7 to 10 or prepared according to the method of any one of claims 1 to 6 as a catalyst, in particular for phenol synthesis.