Isocyanide complexes amines

The reaction of the gold(I) pentafluorophenyl isocyanide complexes with primary and secondary amines as well as alcohols leads to the corresponding gold(I) [62, 65] carbenes (Table 3.2). The addition of amines leads to the corresponding carbenes... 

The majority of gold(I) carbene complexes are pure organometallic compounds and the are out of the scope of this work. Some halide or triphenylphosphine carbene complexes are known and they will be considered here. Nucleophilic addition of alcohols or amines to gold-coordinated isocyanides is one of the best-established methods to obtain gold carbene derivatives. The reaction of H[Au(CN)2] with propene oxide and estirene oxide yields (cyano)carbene complexes (380) avoiding the intermediate step.2257 A cyclic carbene compound is obtained by reaction of a dinuclear isocyanide with amine (Scheme 32).2258... 

Transition metal isocyanide complexes can undergo reactions with nucleophiles to generate carbene complexes. Pt(II) and Pd(II) complexes have been most extensively investigated, and the range of nucleophilic reagents employed in these reactions has included alcohols, amines, and thiols (56) ... 

In a three-component reaction, a cationic platinum isocyanide complex [(Ph3P)2Pt(CNR)Cl][BF4] is reacted with a /3-bromoamine and butyl lithium to give an imidazoldin-2-ylidene complex.This transformation can be a two-component reaction if the isocyanide ligand contains already the necessary amine functionality. This was shown for chromium, molybdenum, tungsten, and rhenium carbonyls. 

The reaction of a series of thiocarbonyl compounds with primary amines has given isocyanide complexes via the intermediate carbene (13) (100). 

Group IV Donors. C-donor ligands. Treatment of [Ru(CN)6]4- with dimethylsulphate for 6h at 95 °C has produced the white isocyanide complex [Ru(CNMe)6]2 +. 67 Electrochemical studies showed that the corresponding Ru,u species can only exist under strongly oxidizing conditions. Furthermore, addition of simple amines to [Ru(CNMe)6]2+ produces either (11) or (12) (containing either uni- or bi-dentate... 

Palladium isocyanide complexes react with amines and alcohols to give palladium Carbene Complexes (equation 15) in a reaction that is a nucleophihc attack on the isonitrile carbon. These complexes easily lose a halide if it is trans to the carbene hgand, since the carbene carbon has a high trans influence. The structures of these compounds have the carbene carbon and its two heteroatom groups in one plane, which is perpendicular to the coordination plane of the Pd. 

Finally, other reactions can be performed directly using water as a solvent. Ugi s four components reaction, for example, provides an expedient access to peptidic scaffolds starting from an isocyanide, an amine, an aldehyde and a carboxylic acid. However, in competition to Ugi s reaction, Passerini ester formation often pollutes the reaction mixture and it is of great interest to perform this type of highly complex transformation in supported versions. Indeed, when an ammonium chloride supported aldehyde, similar to those used in Grieco s multicomponent reactions, are dissolved in water in the presence of an amine, the imine formation occurs within 15 min and isocyanide and acid can subsequently be added to the mixture. After 24 h at room temperature, amides were isolated in high yield with no other purification than washing with diethyl ether [135] (Fig. 44). 

Isocyanide complexes of the stoicheiometry HgCl2,CNR have been prepared, and are postulated to be dimeric and halide-bridged with tetrahedral mercury co-ordination they react with primary and secondary amines to yield guanidines or with AC2CH2 to yield furans through redox decomposition reactions. ... 

Finally nitrile or isocyanide complexes may be attacked. Thus nitrile complexes with aromatic amines and alcohols give complexes of amidines and imidate esters respectively,298 e.g.,... 

It has been shown that these carbenes can insert into Fe-Npor bonds to form vinylidine (A(-alkyl-iron porphyrin metallacycle (N-C-C-Fe)) complexes, " which can then go on to form c/s-bridged vinylidines of the porphyrin, with loss of iron. Carbene equivalents of iodosylbenzene can also react with iron porphyrins to give five-membered Fe-O-C-C-N metallocycles. Iron porphyrin carbenes can also react with amines to produce the isocyanide complexes (equation 58) ... 

Organogold carbene compounds [Au(carbene)(CN) j iR ] can be obtained from com-plexed cyanides [Au(CN)m(C6F5) ] (n = 1 or 3, m = 1 and n = m = 2) by sequential alkylation (to form isocyanide complexes) and nucleophilic attack of amine" . Gold(III) diisocyanides [Au(CNR)2(CgF5)2]+ (R = Ph or p-tolyl), which can also be obtained by isocyanide substitution of ether in [Au(C6F5)2(OEt2)2] > react with hydrazobenzene NH(Ph)NHPh and hydrazine or phenyUiydrazine according to the reactions in Scheme 32 to furnish cyclic bis(carbene) and cyclic carbene-imidoyl compounds . ... 

The dichlorocarbene complex (TPP)Fe(CCl2) is a useful synthetic intermediate forming isocyanide complexes upon reaction with primary amines (Eq. 14) [106]. 

Tertiary, secondary and primary amines add at the SMe2-protected p-C atom to give a variety of ammonium salt, aminocarbene and isocyanide complexes. These latter are formed upon elimination of HCN from the aminocarbene Fe2 p-C(CN)NHR (p-CO)(CO)2Cp2]... 

Primary amines react with [M(CO)5(CS)] to form isocyanide complexes carbene complexes are probably formed as intermediates ... 

The reactions of isocyanide complexes with nucleophiles parallel the reactions of metal carbonyls. Alcohols were found to add across the carbon-nitrogen bond of complexed isocyanides (Badley et al., 1969, 1971). Amines... 

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