Dempsey, Jillian L. and Winkler, Jay R. and Gray, Harry B. (2011) Redox reactivity of photogenerated osmium(II) complexes. Dalton Transactions, 2011 (40). pp. 10633-10636. ISSN 1477-9226. doi:10.1039/C1DT11138H. https://resolver.caltech.edu/CaltechAUTHORS:20110916-103243483
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Abstract
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 of photogenerated Os(II) complexes with methyl viologen to form methyl viologen radical cation and [Os^(III)(NH_3)_5L]^(3+) were monitored by transient absorption spectroscopy. Rate constants range from 4.9 × 10^4 M^(−1) s^(−1) in acetonitrile solution to 3.2 × 10^7 (pH 3) and 2.5 × 10^8 M^(−1) s^(−1) (pH 12) in aqueous media. Photogeneration of five-coordinate Os(II) complexes opens the way for mechanistic investigations of activation/reduction of CO_2 and other relatively inert molecules.
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| Additional Information: | © 2011 The Royal Society of Chemistry. Received 16th June 2011, Accepted 8th August 2011. First published on the web 02 September 2011. This research was supported by an NSF Center for Chemical Innovation (CHE-0802907), the Arnold and Mabel Beckman Foundation, and CCSER (Gordon and Betty Moore Foundation). | |||||||||
| Group: | CCI Solar Fuels | |||||||||
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| Issue or Number: | 40 | |||||||||
| DOI: | 10.1039/C1DT11138H | |||||||||
| Record Number: | CaltechAUTHORS:20110916-103243483 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20110916-103243483 | |||||||||
| Official Citation: | Redox reactivity of photogenerated osmium(II) complexes Jillian L. Dempsey, Jay R. Winkler and Harry B. Gray Dalton Trans., 2011, Advance Article DOI: 10.1039/C1DT11138H, Paper | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 25353 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 24 Oct 2011 18:46 | |||||||||
| Last Modified: | 09 Nov 2021 16:32 |
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