Hydrogen oxidation and production using nickel-based molecular catalysts with positioned proton relays

Aaron D. Wilson, Rachel H. Newell, Michael J. McNevin, James Muckerman, M. Rakowski DuBois, Daniel L DuBois

Research output: Contribution to journalArticle

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Abstract

Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [NI(PPh 2NPh2)2(CH 3CN)](BF4)2, 6a, (where PPh 2NPh 2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7- diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 Å. The cation of [Ni(PCy 2NBz 2)2](BF4) 2, 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six-membered rings formed upon coordination of the diphosphine ligands to the metal are in the boat form. In this case, the average Ni- - -N distance to the pendant base is 3.3 Å. Complex 6a is an electrocatalyst for hydrogen production in acidic acetonitrile solutions, and compound 6b is an electrocatalyst for hydrogen oxidation in basic acetonitrile solutions. It is demonstrated that the high catalytic rates observed with these complexes are a result of the positioning of the nitrogen base so that it plays an important role in the formation and cleavage of the H-H bond.

Original languageEnglish
Pages (from-to)358-366
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number1
DOIs
Publication statusPublished - Jan 11 2006

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Nickel
Protons
Hydrogen
Ligands
Electrocatalysts
Oxidation
Catalysts
Acetonitrile
Nitrogen
Ships
Boats
Cations
Positive ions
Atoms
Hydrogen production
X-Ray Diffraction
Phosphorus
Conformations
Metals
Air

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Hydrogen oxidation and production using nickel-based molecular catalysts with positioned proton relays. / Wilson, Aaron D.; Newell, Rachel H.; McNevin, Michael J.; Muckerman, James; DuBois, M. Rakowski; DuBois, Daniel L.

In: Journal of the American Chemical Society, Vol. 128, No. 1, 11.01.2006, p. 358-366.

Research output: Contribution to journalArticle

Wilson, Aaron D. ; Newell, Rachel H. ; McNevin, Michael J. ; Muckerman, James ; DuBois, M. Rakowski ; DuBois, Daniel L. / Hydrogen oxidation and production using nickel-based molecular catalysts with positioned proton relays. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 1. pp. 358-366.
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N2 - Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [NI(PPh 2NPh2)2(CH 3CN)](BF4)2, 6a, (where PPh 2NPh 2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7- diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 Å. The cation of [Ni(PCy 2NBz 2)2](BF4) 2, 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six-membered rings formed upon coordination of the diphosphine ligands to the metal are in the boat form. In this case, the average Ni- - -N distance to the pendant base is 3.3 Å. Complex 6a is an electrocatalyst for hydrogen production in acidic acetonitrile solutions, and compound 6b is an electrocatalyst for hydrogen oxidation in basic acetonitrile solutions. It is demonstrated that the high catalytic rates observed with these complexes are a result of the positioning of the nitrogen base so that it plays an important role in the formation and cleavage of the H-H bond.

AB - Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [NI(PPh 2NPh2)2(CH 3CN)](BF4)2, 6a, (where PPh 2NPh 2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7- diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 Å. The cation of [Ni(PCy 2NBz 2)2](BF4) 2, 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six-membered rings formed upon coordination of the diphosphine ligands to the metal are in the boat form. In this case, the average Ni- - -N distance to the pendant base is 3.3 Å. Complex 6a is an electrocatalyst for hydrogen production in acidic acetonitrile solutions, and compound 6b is an electrocatalyst for hydrogen oxidation in basic acetonitrile solutions. It is demonstrated that the high catalytic rates observed with these complexes are a result of the positioning of the nitrogen base so that it plays an important role in the formation and cleavage of the H-H bond.

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