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Tin(iv) and lead(iv) complexes with a tetradentate redox-active ligand
Authors:Piskunov Alexandr V  Trofimova Olesya Yu  Fukin Georgy K  Ketkov Sergei Yu  Smolyaninov Ivan V  Cherkasov Vladimir K
Institution:G.A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, Tropinina str. 49, 603950, Nizhny Novgorod, Russia. pial@iomc.ras.ru.
Abstract:The coordination chemistry of a tetradentate redox-active ligand, glyoxal-bis(2-hydroxy-3,5-di-tert-butylanil) (H(2)L), was investigated with the diorganotin(iv) and diphenyllead(iv) moieties. Complexes R(2)SnL (R = Me (), Et (), (t)Bu (), Ph ()) and Ph(2)PbL () have been prepared and characterized. The molecular structures of compounds , and have been determined by single crystal X-ray diffraction. The diamagnetic octahedral complexes bear a tetradentate O,N,N,O redox-active ligand with a nearly planar core. Complexes demonstrate solvatochromism in solution. The CV of complexes reveals four one-electron redox processes. The spin density distribution in the chemically generated cations and anions of was studied by X-band EPR spectroscopy. The experimental data agree well with the results of DFT calculations of electronic structures for , its pyridine adduct ·Py, cation and anion .
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