期刊
ORGANOMETALLICS
卷 29, 期 21, 页码 5390-5401出版社
AMER CHEMICAL SOC
DOI: 10.1021/om100395r
关键词
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资金
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
The cyclic diphosphine ligands (P2N2ph)-N-tBu and (P2N2Bz)-N-tBu have been synthesized and used to prepare new complexes of Co(II) and Ni(II) with the formula [M((P2N2R)-N-tBu)(CH3CNn](BF4)(2) (n = 2,3). The products have been characterized by variable-temperature NM R data, X-ray diffraction studies, and cyclic voltammetry, and properties of the new complexes have been compared with those of previously studied complexes containing (P2N2R)-N-ph 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((P2N2Ph)-N-tBu)(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) an overpotential of 160 mV. These cobalt derivatives are a promising class of catalysts for further study and optimization.
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