Photochemical Reductive trans-Elimination from trans-Diacidotetracyanoplatinate(IV) Complexes
Open Access
- 1 November 1978
- journal article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung B
- Vol. 33 (11) , 1352-1356
- https://doi.org/10.1515/znb-1978-1132
Abstract
Upon CT excitation the complex ions trans-[Pt(CN)4N3X]2- and trans-[Pt(CN)4X2]2- (X = Cl and Br) undergo a reductive trans-elimination with formation of [Pt(CN)4]2- and two ligand radicals in the photoprimary step. The formation of a Pt(III) intermediate is not observed. Due to the stability of [Pt(CN)4]2-, recombination reactions regenerating the starting complex are efficient if the ligand radicals are not scavenged. For the azide complexes the high quantum yields for the production of [Pt(CN)4]2- are explained by the instability of azide radicals. For trans-[Pt(CN)4X2]2-, the recombination is efficient in aqueous solution, while in ethanol the halogen atoms are scavenged by hydrogen abstraction. The sequence of steps following CT excitation can be explained by a potential energy diagram.Keywords
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