A New Approach to Nitrogen Fixation. Protonation of Dinitrogen Ligand by means of Hydridometal Carbonyls and the Synthesis of Alkoxide Hydrazido(2-) Complexes of Tungsten with Iron and Cobalt Carbonyl Complex Anions

Article abstract of DOI:10.1021/ja00380a010

Treatment of cis- with an acidic hydridometal carbonyl, HFeCo3(CO)12, H2Fe(CO)4, or HCo(CO)4, in methanol followed by KOH distillation formed ammonia and hydrazine in moderate yields.The influence of a hydrogen atmosphere upon improvement of the yields is significant.The formation of ammonia and hydrazine from cis- was negligibly small.Reactions of trans- (dpe) = 1,2-bis(diphenylphosphino)ethane) with the hydride complexes in an alcohol gave alkoxide hydrazido(2-) complexes of the type trans-⁺A^-.The following combinations were used: A = FeCo3(CO)12, R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, sec-C4H9, c-C6H11, n-C6H13, and CH2C6H5; A = Co(CO)4, R = CH3, C2H5; A = Co3(CO)10, R = CH3.Alkoxide complexes ^+- and ^+- were obtained from trans-.The role of the hydridometal carbonyls and of the alcohols in the protonation reaction of the coordinated dinitrogen is discussed.