Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2'-Azobispyridine: Formation of Cyclic (m,h2:h1-abpy)PtCl22+ with a New Coordination Mode for abpy and a Near-Infrared Ligand-to-Ligand Intervalence Charge Transfer Absorption of the One-Electron Reduced State

, , , , , , , , und . Inorganic Chemistry 43 (19): 5973--5980 (2004)


The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand p interaction as supported by DFT calcns. Unexpectedly, its chem. or electrochem. redn. occurs irreversibly to yield EPR-detectable (μ,η2:η2-abpy)PtCl22.bul.- and, as the main product of chloride dissocn., the structurally identified and DFT-calcd. dinuclear (m,h2:h1-abpy)PtCl22+ with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible 1-electron redn. of that dimer, sepd. by 0.24 V, exhibits an intense near-IR band for the monocationic intermediate (abpy-I)(abpy)Pt2Cl2.bul.+ at 1220 nm (e = 3370 M-1 cm-1) which is attributed to a ligand-to-ligand intervalence charge-transfer transition. on SciFinder(R)

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