Oxidation by Oxygen and Sulfur of Tin(IV) Derivatives Containing a Redox-Active o-Amidophenolate Ligand
✍ Scribed by Alexandr V. Piskunov; Irina N. Mescheryakova; Georgii K. Fukin; Evgenii V. Baranov; Markus Hummert; Andrei S. Shavyrin; Vladimir K. Cherkasov; Gleb A. Abakumov
- Publisher
- John Wiley and Sons
- Year
- 2008
- Tongue
- English
- Weight
- 415 KB
- Volume
- 14
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
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.