Short-lived intermediates in photochemistry of an OsCl62- complex in aqueous solutions

Marina V Rogozina; Vladislav V Yudanov; Roman G Fedunov; Ivan P Pozdnyakov; Alexey A Melnikov; Sergey V Chekalin; Evgeni M Glebov

doi:10.1039/c7pp00299h

Short-lived intermediates in photochemistry of an OsCl₆^2- complex in aqueous solutions

Photochem Photobiol Sci. 2018 Jan 17;17(1):18-26. doi: 10.1039/c7pp00299h.

Authors

Marina V Rogozina¹, Vladislav V Yudanov, Roman G Fedunov, Ivan P Pozdnyakov, Alexey A Melnikov, Sergey V Chekalin, Evgeni M Glebov

Affiliation

¹ Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., 630090, Novosibirsk, Russian Federation. glebov@kinetics.nsc.ru.

PMID: 29143059
DOI: 10.1039/c7pp00299h

Abstract

Two mechanisms of Os^IVCl₆^2- photolysis were studied by means of quantum chemical calculations in gas and aqueous phases. The difference between these mechanisms is in the nature of the possible Os(iv) key intermediates (KI). According to calculations, the intermediate is an Os^IVCl₅^- complex of square pyramidal coordination geometry. The calculations do not give an opportunity to make an unambiguous choice between the triplet and quintet multiplicities of Os^IVCl₅^-. The calculated CASSCF/IMCP-SR1 transition energies for ⁵Os^IVCl₅^- are lower than for ³Os^IVCl₅^-, while the calculated XMC-QDPT2/SBKJC spectra for the triplet state are in better agreement with the experimental absorption spectrum of the KI than for the quintet state.