Isocyanide complexes with 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 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... 

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. 

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.,... 

---