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

Aaron D. Wilson, R. K. Shoemaker, A. Miedaner, James Muckerman, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

253 Citations (Scopus)

Abstract

Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2 PhN2 Ph) 2(CH3CN)](BF4)2, 3a (where P 2 PhN2 Ph is 1,3,5,7-tetraphenyl-1,5- diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s-1 establishes that the rate of H2 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(P2 CyN2 Bz)2](BF4) 2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm-1 at 25°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 1H, 31P, and 15N NMR spectroscopies as Ni(0) 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 CyN2 Bz)2](BF 4), 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.

Original languageEnglish
Pages (from-to)6951-6956
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume104
Issue number17
DOIs
Publication statusPublished - Apr 24 2007

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phosphine
Hydrogen
Nitrogen
Ligands
Nickel
Protons
Amines
Magnetic Resonance Spectroscopy
Electrons

Keywords

  • Catalysis
  • Hydrogen oxidation
  • Hydrogen production

ASJC Scopus subject areas

  • Genetics
  • General

Cite this

Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases. / Wilson, Aaron D.; Shoemaker, R. K.; Miedaner, A.; Muckerman, James; DuBois, Daniel L; DuBois, M. Rakowski.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 104, No. 17, 24.04.2007, p. 6951-6956.

Research output: Contribution to journalArticle

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abstract = "Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2 PhN2 Ph) 2(CH3CN)](BF4)2, 3a (where P 2 PhN2 Ph is 1,3,5,7-tetraphenyl-1,5- diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s-1 establishes that the rate of H2 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(P2 CyN2 Bz)2](BF4) 2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm-1 at 25°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 1H, 31P, and 15N NMR spectroscopies as Ni(0) 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 CyN2 Bz)2](BF 4), 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.",
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N2 - Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2 PhN2 Ph) 2(CH3CN)](BF4)2, 3a (where P 2 PhN2 Ph is 1,3,5,7-tetraphenyl-1,5- diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s-1 establishes that the rate of H2 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(P2 CyN2 Bz)2](BF4) 2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm-1 at 25°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 1H, 31P, and 15N NMR spectroscopies as Ni(0) 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 CyN2 Bz)2](BF 4), 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.

AB - Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2 PhN2 Ph) 2(CH3CN)](BF4)2, 3a (where P 2 PhN2 Ph is 1,3,5,7-tetraphenyl-1,5- diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s-1 establishes that the rate of H2 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(P2 CyN2 Bz)2](BF4) 2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm-1 at 25°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 1H, 31P, and 15N NMR spectroscopies as Ni(0) 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 CyN2 Bz)2](BF 4), 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.

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