Electroreduction of co-ordinated cyanide to the aminocarbyne ligand (CNH2) and a pathway for isomerisation of ligating methyleneamide (NCH2): reactions at molybdenum of relevance to cyanide reduction by nitrogenase

Abstract

Electroreduction of trans-[Mo(CN)Cl(Ph₂PCH₂CH₂ PPh₂)₂] in the presence of phenol gives trans-[Mo(CNH₂)Cl(Ph₂PCH₂ CH₂PPh₂)₂], this is the first example of the conversion of co-ordinated cyanide to the aminocarbyne ligand, a reaction of relevance to reduction of cyanide by nitrogenase; the methyleneamide, trans-[Mo(NCH₂)Cl(Ph₂PCH₂ CH₂PPh₂)₂], is oxidised to the cyanide and therefore the redox reactions provide a pathway for the isomerisation of the group (MoNCH₂) to (MoCNH₂).