Complex reduction chemistry of (abpy)PtCl2, abpy = 2,2'-azobispyridine: formation of cyclic [(micro,eta2:eta1-abpy)PtCl]2(2+) with a new coordination mode for abpy and a near-infrared ligand-to-ligand intervalence charge transfer absorption of the one-electron reduced state

Inorganic Chemistry
Akbey DoganWolfgang Kaim

Abstract

The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand pi interaction as supported by DFT calculations. Unexpectedly, its chemical or electrochemical reduction occurs irreversibly to yield EPR-detectable [(micro,eta2:eta2-abpy)[PtCl2]2]*- and, as the main product of chloride dissociation, the structurally identified and DFT-calculated dinuclear [(micro,eta2:eta1-abpy)PtCl]2(2+) with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible one-electron reduction of that dimer, separated by 0.24 V, exhibits an intense near-infrared band for the monocationic intermediate [(abpy(-I))(abpy)Pt2Cl2]*+ at 1220 nm (epsilon = 3370 M(-1) cm(-1)) which is attributed to a ligand-to-ligand intervalence charge-transfer transition.

Citations

Feb 3, 2009·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Zhiping ZhuangBing Zhao
Sep 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·J Pérez-MiqueoZ Freixa
Aug 8, 2018·Chemistry : a European Journal·Jarl Ivar van der Vlugt
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·David SchweinfurthBiprajit Sarkar
Nov 30, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Naina DeibelBiprajit Sarkar
Feb 1, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Manuel BardajíPablo Espinet
Mar 7, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Amit KumarDaya Shankar Pandey
Mar 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Mina HanYumi Okui
Nov 7, 2006·Inorganic Chemistry·Stefan DeekenRhett Kempe
Mar 30, 2021·Chemistry : a European Journal·Jonathan LongNicolas Bogliotti

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