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Photochemistry of hexachloroosmate(IV) in ethanol
Evgeni M Glebov1, Svetlana G Matveeva2, Ivan P Pozdnyakov1
1V.V. Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., 630090, Novosibirsk, Russian Federation. glebov@kinetics.nsc.ru and Novosibirsk State University, 2 Pirogova Str., 630090, Novosibirsk, Russian Federation.
Abstract:
The photochemistry of the OsIVCl62- complex in ethanol was studied by means of stationary photolysis, nanosecond laser flash photolysis, ultrafast pump-probe spectroscopy and quantum chemistry. The direction of the photochemical process was found to be wavelength-dependent. Irradiation in the region of the d-d and LMCT bands results in the photosolvation (with the wavelength-dependent quantum yield) and photoreduction of Os(iv) to Os(iii), correspondingly. The characteristic time of photosolvation is ca. 40 ps. Photoreduction occurs in the micro- and millisecond time domains via several Os(iii) intermediates. The nature of intermediates and the possible mechanisms of photoreduction are discussed. We believe that the lability of the photochemically produced Os(iv) and Os(iii) intermediates determines the synthetic potential of OsIVCl62- photochemistry.
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