Isocyanide ligands synthesis

A number of routes have been employed for the synthesis of metal isocyanide complexes by generating the isocyanide ligand on the metal atom. 

Examples in organocopper chemistry are the synthesis of h -cyclopentadienyl-copper complexes with phosphite, phosphine or isocyanide ligands via the reaction of h -CjHjTl with Cu(I) halide-ligand complexes in pentane or THE at 25°C . 

Amino-substituted Fischer carbene complexes can also be prepared from isocyanide complexes. This synthesis is less common than the synthesis of alkoxy-substituted carbenes because there are fewer appropriate isocyanide complexes to use as reactants than there are carbonyl complexes, and isocyanide ligands are less electrophilic. Thus, this reaction sequence has often been conducted intramolecularly to promote attack on the isocyanide ligand instead of an ancillary carbonyl group. An intramolecular example of the synthesis of an amino-substituted carbene by attack of an isocyanide ligand is shown in Equation 13.3, ... 

The first synthesis of a complex containing a metal-carbon triple bond was reported in 1973 [1]. Since then, numerous carbyne complexes have been prepared. In recent years, the study of the reactivity of these complexes has attracted considerable interest [2]. E.g. carbyne complexes have extensively been used as building blocks in the synthesis of transition metal clusters [3]. The coupling of carbyne ligands with CO or isocyanide ligands has also been studied in detail [4]. However, the number of reports on the use of carbyne complexes in synthetic organic chemistry is rather limit in contrast to carbene complexes which have found many applications in the synthesis of carbo- and heterocycles [5]. 

Until the appearance of a recent communication 37), no zero-valent ruthenium isocyanide complexes had been described. The synthesis of these complexes was accomplished by a lengthy reaction sequence, which was necessary since simple reactions such as substitution of a ligand in... 

Erker and Trinkl synthesized the tricycles 177 as novel GABA-A/benzodiazepine receptor ligands via synthesis of enol phosphates such as 175 and reaction with isocyanides 176 (Scheme 13) <2001H1963>. 

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