Nitrosyl complexes reaction with carbon monoxide

Carmona et al. (899) prepared another monomeric molybdenum(I) nitrosyl complex, mer-[Mo(NO)(PMe3)3(S2CNMe2)], from [MoCl(NO)(PMe3)4]. Further reaction with carbon monoxide yields frani-[Mo(NO)(CO)(S2CNMe2)(PMe3)2] via replacement of the phosphine trans to a molybdenum-sulfur bond (Eq. 78). 

The reaction of nitrite complexes with carbon monoxide to yield the metal nitrosyl complex and carbon dioxide has been known for a consider-... 

Nitrosyls.— Treatment of the nitrosyl complex [Ir(NO)2(PPh3)2] lPFe] with carbon monoxide results in the formation of COg and NjO and [Ir(CO)3(PPh8)a] [PF6l The initial step in this reaction is believed to involve the coupling of two NO ligands to generate the intermediate The overall sequence shown in Scheme 2 is proposed. 

Formation of Ni(CO)4 or Co(CO)4- by the cyanide method depends upon the stepwise substitution of the anion of the cyano complex by the iso-electronic carbon monoxide molecule. By treating Co2(CO)8 with potassium cyanide we obtained cyanocarbonyls of cobalt of low oxidation number (83). In reactions of the nitrosyl carbonyls of iron and cobalt, Behrens (86) substituted all the CO groups with CN to give K3[Co(NO)(CN)3] or... 

Wang X, Zhou M, Andrews L (2000) Reactions of iron atoms with nitric oxide and carbon monoxide in excess argon infrared spectra and density functional calculations of iron carbonyl nitrosyl complexes. J Phys Chem A 104 10104-10111... 

Reaction of the nitrosylcarbonyl complex, [Mo(CO)2NOCp], with PPha results in the formation of [Mo(NCO)(CO)(PPha)2Cp], along with other reaction products. 56 The reaction pathway involves deoxygenation of the nitrosyl ligand and generation, from the nitrosyl, of an organometallic nitrene which then captures carbon monoxide to form isocyanate. 

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