Abstract
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)[PtCl2]2.bul.- and, as the main product of chloride dissocn., the structurally identified and DFT-calcd. dinuclear [(m,h2:h1-abpy)PtCl]22+ 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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