Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases.

ABSTRACT: Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H(2) have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P(2)(Ph)N(2)(Ph))(2)(CH(3)CN)](BF(4))(2), 3a (where P(2)(Ph)N(2)(Ph) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane), permits a limiting value of the H(2) production rate to be determined. The turnover frequency of 350 s(-1) establishes that the rate of H(2) production for the mononuclear nickel catalyst 3a is comparable to those observed for Ni-Fe hydrogenase enzymes. In the electrochemical oxidation of hydrogen catalyzed by [Ni(P(2)(Cy)N(2)(Bz))(2)](BF(4))(2), 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition o

SUBMITTER: Wilson AD 

PROVIDER: S-EPMC1855379 | biostudies-literature | 2007 Apr

REPOSITORIES: biostudies-literature