期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 104, 期 17, 页码 6951-6956出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0608928104
关键词
catalysis; hydrogen oxidation; hydrogen production
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((P2N2Ph)-N-Ph)(2)(CH3CN)](BF4)(2), 3a (where (P2N2Ph)-N-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((P2N2Bz)-N-Cy)(2)](BF4)(2), 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (K-eq = 190 atm(-1) at 25 degrees C). The hydrogen addition product exists as three nearly isoenergetic isomers 4A-4C, which have been identified by a combination of one- and two-dimensional H-1, P-31, and N-15 NMR spectroscopies as Ni(O) complexes with a protonated amine in each cyclic ligand. The nature of the isomers, together with calculations, suggests a mode of hydrogen activation that involves a symmetrical interaction of a nickel dihydrogen ligand with two amine bases in the diphosphine ligands. Single deprotonation of 4 by an external base results in a rearrangement to [HNi(P(2)(Cy)N(2)Bz)(2)](BF4), 5, and this reaction is reversed by the addition of a proton to the nickel hydride complex. The small energy differences associated with significantly different distributions in electron density and protons within these molecules may contribute to their high catalytic activity.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据