Organic isocyanide

Zerovalent transition metal complexes of organic isocyanides. Y. Yamamoto, Coord. Chem. Rev., 1980,32,193-233 (172). 

The Si=As bond reacts with organic isocyanides in the same way that the Si=P bond does. Thus, with mesityl isocyanide and 1,6-diisocyano-hexane 44a forms the unusual arsaalkene derivatives 53 and 54, according to Scheme 14. Their molecular structures were determined by X-ray crystallography.39,40... 

Organic isocyanides (C=N-R) are versatile ligands in transition metal complex chemistry. As compared with their pseudo-isoelectronic cousin, C=0, they are stronger o-donors [1], As a result, isocyanides form more stable complexes with metals in relatively high oxidation states (e.g., +2 and +3) than CO. In contrast, they have a lower ir-accepting ability than CO and therefore form less stable complexes with metals in low oxidation states (e.g., -1 and -2). Nevertheless, they form a broad range of metal complexes, and various aspects of their syntheses, structures and bonding have been reviewed [1-7]. 

Only more recent investigations of organic isocyanide complexes of chromium are in this section, because general synthetic methods for metal isocyanide complexes, including mixed carbonyl isocyanides, and the nature of the metal-isocyanide bond are discussed in Sections... 

Cyanide and organic isocyanide complexes of chromium(ll) have been included with th lower oxidation states in Sections 35.2.1.1 and 35.2.1.2. 

The chromium(II) hydride [CrH2 P(OMe)3 s] is fluxional and the seven-coordinate structure (20) is likely from an analysis of the 31P and XH NMR spectra (Table 21).125 Some mixed ligand complexes with organic isocyanides are given in Table 3. 

Treatment of (22) with CbH = carbazole (38) in hydrocarbon solvents gave [Cb2M]2(/x2-CR)2 ((39) Scheme 4). The reactivity of this species towards hydrogenation (M = Ta) and to organic isocyanides was studied.69,70 Reaction of (39) with 1 eq EtC=CEt produced the di-metallacyclic compound (40) by alkyne insertion into one of the bridging alkylidyne groups.71,72... 

Analytical aspects of triple-bonded functional groups TABLE 4. Industrial organic isocyanides ... 

TABLE 6. Complexes of organic isocyanides with transition metals... 

Some mixed ligand complexes with organic isocyanides are given in Table 3. 

The insertion chemistry of the di-alkyls [Cp(ArO)Zr(CH2Ph)2] with organic isocyanides also leads to mono- and bis-fj -iminoacyl derivatives. Their spectroscopic and structural parameters are very similar to the corresponding bis-aryloxides. " ... 

A number of such complexes have been prepared (Table II), the usual method of preparation being the action of organic isocyanides on iron or cobalt nitrosyl carbonyls, or on other nitrosyl complexes. The dipole moments of a number of the products have been measured (Table VI). 

Kim Y-J, Lee S-H, Lee S-H, Jeon SI, Lim MS, Lee SW (2005) Reactivity of alkynyl Pd(II) azido complexes toward organic isocyanides, isothiocyanates, and nitriles. Inoig Chim Acta... 

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