Comparison of cobalt and nickel complexes with sterically demanding cyclic diphosphine ligands: Electrocatalytic H2 production by [Co(P tBu 2NPh 2)(CH3CN) 3](BF4)2

Eric Wiedner, Jenny Y. Yang, William G. Dougherty, W. Scott Kassel, R Morris Bullock, M. Rakowski Dubois, Daniel L DuBois

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Abstract

The cyclic diphosphine ligands PtBu 2N Ph 2 and PtBu 2N Bz 2 have been synthesized and used to prepare new complexes of Co(II) and Ni(II) with the formula [M(Pt Bu 2NR 2)(CH3CN) n](BF4)2 (n = 2, 3). The products have been characterized by variable-temperature NMR data, X-ray diffraction studies, and cyclic voltammetry, and properties of the new complexes have been compared with those of previously studied complexes containing PPh 2NR 2 ligands. The variation of either phosphorus or nitrogen substituents in these ligands can result in significant differences in the structure, electrochemistry, and reactivity of the metal complexes. [Co(PtBu 2NPh 2)(CH3CN)3](BF4)2 is found to be an effective electrocatalyst for the formation of hydrogen using bromoanilinium tetrafluoroborate as the acid, with a turnover frequency of 160 s-1 and an overpotential of 160 mV. These cobalt derivatives are a promising class of catalysts for further study and optimization.

Original languageEnglish
Pages (from-to)5390-5401
Number of pages12
JournalOrganometallics
Volume29
Issue number21
DOIs
Publication statusPublished - Nov 8 2010

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Cobalt
Nickel
cobalt
nickel
Ligands
ligands
electrocatalysts
Electrocatalysts
Coordination Complexes
Electrochemistry
electrochemistry
Phosphorus
Cyclic voltammetry
phosphorus
Hydrogen
Nitrogen
reactivity
Nuclear magnetic resonance
Derivatives
nitrogen

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Comparison of cobalt and nickel complexes with sterically demanding cyclic diphosphine ligands : Electrocatalytic H2 production by [Co(P tBu 2NPh 2)(CH3CN) 3](BF4)2. / Wiedner, Eric; Yang, Jenny Y.; Dougherty, William G.; Kassel, W. Scott; Bullock, R Morris; Dubois, M. Rakowski; DuBois, Daniel L.

In: Organometallics, Vol. 29, No. 21, 08.11.2010, p. 5390-5401.

Research output: Contribution to journalArticle

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N2 - The cyclic diphosphine ligands PtBu 2N Ph 2 and PtBu 2N Bz 2 have been synthesized and used to prepare new complexes of Co(II) and Ni(II) with the formula [M(Pt Bu 2NR 2)(CH3CN) n](BF4)2 (n = 2, 3). The products have been characterized by variable-temperature NMR data, X-ray diffraction studies, and cyclic voltammetry, and properties of the new complexes have been compared with those of previously studied complexes containing PPh 2NR 2 ligands. The variation of either phosphorus or nitrogen substituents in these ligands can result in significant differences in the structure, electrochemistry, and reactivity of the metal complexes. [Co(PtBu 2NPh 2)(CH3CN)3](BF4)2 is found to be an effective electrocatalyst for the formation of hydrogen using bromoanilinium tetrafluoroborate as the acid, with a turnover frequency of 160 s-1 and an overpotential of 160 mV. These cobalt derivatives are a promising class of catalysts for further study and optimization.

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