Metal-Oxo Photo-oxidants, Photochemistry and Photophysics of trans-[Os^(VI)(tmc)(O)_2]^(2+)(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[Os^(VI)(CN)_4(O)_2]^(2-)

Che, Chi-Ming and Yam, Vivian Wing-Wah and Cho, Kar-Cheong and Gray, Harry B. (1987) Metal-Oxo Photo-oxidants, Photochemistry and Photophysics of trans-[Os^(VI)(tmc)(O)_2]^(2+)(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[Os^(VI)(CN)_4(O)_2]^(2-). Journal of the Chemical Society. Chemical Communications (12). pp. 948-949. ISSN 0022-4936 http://resolver.caltech.edu/CaltechAUTHORS:20120627-100742357

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Abstract

trans-[Os^(VI)(tmc)(O)_2]^(2+)(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[Os^(VI)(CN)_4(O)_2]^(2-) are emissive in the solid state and in fluid solutions at room temperature (τ~ 1.0–1.5 µs); the (^3)E_g state of trans-[Os^(VI)(tmc)(O)_2]^(2+) is a powerful one-electron oxidant {[Os^(VI)(O)_2]^(2+) + e^– → [Os^V (O)_2]+, E^0_f > 2.0 V vs. normal hydrogen electrode} in aqueous solution, reacting with PPh3 and ((PhCH_2)_2)S to give O=PPh_3 and ((PhCH_2)_2)S=O, respectively.

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© 1987 Royal Society of Chemistry. Received 11th February 1987; Com. 183. We thank Dr. Janet L. Marshall for experimental assistance. Support from the Croucher Foundation (C. M. C. and V. W.-W. Y.) and National Science Foundation Grant CHE84-19828 (H. B. G.) is gratefully acknowledged. This is contribution No. 7573 from the Arthur Amos Noyes Laboratory. V. W.-W. Y. is a Croucher Foundation and Li Po Chun Scholar.

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Funding Agency	Grant Number
Croucher Foundation	UNSPECIFIED
NSF	CHE-84-19828

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Caltech Arthur Amos Noyes Laboratory	7573

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27 Jun 2012 18:36

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