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).