SYNTHESES AND REACTIVITY OF ORGANOMETALLIC COMPOUNDS CONTAINING IMINOACYL LIGANDS. REACTIONS OF METAL CARBONYL ANIONS WITH IMIDOYL HALIDES

Metal carbonyl anions readily react with imidoyl halides through nucleophilic displacement of the halide atom to produce complexes containing η1-iminoacyl ligands. However, weakly nucleophilic anions, such as tetracarbonylcobaltate, induce a head-to-tail coupling reaction of two imidoyl groupings via the incorporation of two anions. This has been established by an X-ray crystallographic analysis of the compound CO2(CO)5(P(CH3)2C6H5)[(C6H5)CN(C6H5)]2. The bis-imidoyl ligand chelates one cobalt atom while one of the carbon atoms bridges the two mutually bonded cobalt atoms. Photolytic decarbonylation of the complexes containing η1-iminoacyl ligands may proceed by either of three processes. When the substituent on the nitrogen atom is an alkyl group, either a migration with formation of an isocyanide ligand or formation of an η2-iminoacyl ligand can occur. When the substituent is an aryl group, ortho-metallation of the N-aryl ring occurs. This has been demonstrated by an X-ray crystallographic analysis of the compound (C5H5)Fe-(CO)[C(C6H5)N(H)p-CH3C6H3)] which contains a phenyl-N-p-tolylaminocarbene ligand in which the p-tolyl ring is bonded to the iron atom in an ortho position. © 1979, All rights reserved.