title: Oxidation by oxygen and sulfur of Tin(IV) derivatives containing a redox-active o-amidophenolate ligand.
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.
authors.affiliation: G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Street, 603950 Nizhny Novgorod, Russia.
authors.forename: Alexandr V
authors.initials: AV
authors.lastname: Piskunov
authors.forename: Irina N
authors.initials: IN
authors.lastname: Mescheryakova
authors.forename: Georgii K
authors.initials: GK
authors.lastname: Fukin
authors.forename: Evgenii V
authors.initials: EV
authors.lastname: Baranov
authors.forename: Markus
authors.initials: M
authors.lastname: Hummert
authors.forename: Andrei S
authors.initials: AS
authors.lastname: Shavyrin
authors.forename: Vladimir K
authors.initials: VK
authors.lastname: Cherkasov
authors.forename: Gleb A
authors.initials: GA
authors.lastname: Abakumov