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Redox reactivity of photogenerated osmium(II) complexes

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. 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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/C1DT11138H DOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2011/DT/c1dt11138hPublisherArticle
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
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
Funders:
Funding AgencyGrant Number
NSFCHE-0802907
Arnold and Mabel Beckman FoundationUNSPECIFIED
Caltech Center for Sustainable Energy ResearchUNSPECIFIED
Issue or Number:40
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:22 Nov 2019 09:58

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