期刊
INORGANIC CHEMISTRY
卷 50, 期 17, 页码 8630-8635出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic201184x
关键词
-
资金
- Office of Basic Energy Sciences of the U.S. Department of Energy [DE-FG02-07ER15885]
A synthesis has been developed that allows the isolation of four-coordinate [(tpy)Ni-Br] (1, tpy = terpyridine) in high yield. Complex 1 has been structurally characterized, and the X-ray data reveal a square-planar geometry, unlike the known [(tpy')Ni-I] (tpy' = 4,4',4-tri-tert-butyl-terpyridine) but similar to [(tpy)Ni-CH3]. In the solid-state, EPR spectroscopy indicates, however, that unlike [(tpy)Ni-CH3], the electronic structure of 1 is a metal-centered, not a ligand-centered radical. Density functional theory (DFT) analyses support this assignment. The preparation of 1 also facilitated the analysis of the redox potentials of a series of terpyridine nickel derivatives. It was found that the overall ligand sphere (one vs two coordinated terpyridine ligands) plays more of a role in determining the redox potentials of these derivatives than do the formal oxidation states of the nickel ions in the solution phase.
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