Redox reactivity of photogenerated osmium(II) complexes
作者： Jillian L. Dempsey , Jay R. Winkler , Harry B. Gray
DOI: 10.1039/C1DT11138H
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摘要: Powerful reductants [Os^(II)(NH_3)_5(L]^(2+) (L = OH_ 2, CH_3, CN can be generated upon ultraviolet excitation of relatively inert [Os^(II)(NH_3)_5(N_2)]^(2+) in aqueous and acetonitrile solutions. Reactions photogenerated Os(II) complexes with methyl viologen to form radical cation [Os^(III)(NH_3)_5L]^(3+) were monitored by transient absorption spectroscopy. Rate constants range from 4.9 × 10^4 M^(−1) s^(−1) solution 3.2 10^7 (pH 3) 2.5 10^8 12) media. Photogeneration five-coordinate opens the way for mechanistic investigations activation/reduction CO_2 other molecules.
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