Oxidation by oxygen and sulfur of Tin(IV) derivatives containing a redox-active o-amidophenolate ligand |
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Authors: | Piskunov Alexandr V Mescheryakova Irina N Fukin Georgii K Baranov Evgenii V Hummert Markus Shavyrin Andrei S Cherkasov Vladimir K Abakumov Gleb A |
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Institution: | G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Street, 603950 Nizhny Novgorod, Russia. |
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Abstract: | Oxidation of tin(IV) o-amidophenolate complexes Sn(ap)Ph(2)] (1) and Sn(ap)Et(2)(thf)] (2) (ap=dianion of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (ImQ)) with molecular oxygen and sulfur in toluene solutions was investigated. The reaction of oxygen with 1 at room temperature forms a paramagnetic derivative Sn(isq)(2)Ph(2)] (3) (isq=radical anion of ImQ) and diphenyltin(IV) oxide {Ph(2)SnO}(n)]. Interaction of 1 with sulfur gives another monophenyl-substituted paramagnetic tin(IV) complex, Sn(ap)(isq)Ph] (4), and the sulfide, Ph(3)Sn](2)S. The oxidation of 2 with oxygen and with sulfur proceeds through the derivative Sn(isq)(2)Et(2)] (7), which undergoes alkyl elimination to give two new tin(IV) compounds, Sn(ap)(isq)Et] (5) and Sn(ap)(EtImQ)Et] (6) (EtImQ=2,4-di-tert-butyl-6-(2,6-diisopropylphenylimino)-3-ethylcyclohexa-1,4-dienolate ligand), respectively, along with the corresponding alkyltin(IV) oxide and sulfide. Complexes 3-5 and 7 were studied by EPR spectroscopy. The structures of 3, 4 and 6 were investigated by X-ray analysis. |
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Keywords: | N O ligands oxidation reaction mechanisms structure elucidation tin |
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