Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten. (24th November 2015)

• Record Type: Journal Article
• Authors: Fukuda, Tetsuya; Hashimoto, Hisako; Sakaki, Shigeyoshi; Tobita, Hiromi
• Is Part Of: Angewandte Chemie. Volume 128:Number 1(2016)
• Page Start: 196
• Page End: 200
• Publication Date: 2015-11-24
• Subjects: Metallacyclen -- Silaaldehyde -- Silanone -- Silicium -- Wolfram; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201507956
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Treatment of pyridine‐stabilized silylene complexes [(η 5 ‐C5 Me4 R)(CO)2 (H)WSiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3 )3 ) with an N‐heterocyclic carbene Me I i Pr (1, 3‐diisopropyl‐4, 5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η 5 ‐C5 Me4 R)(CO)2 WSiH(Tsi)][H Me I i Pr] (R=Me (1‐Me ); R=Et (1‐Et )). Subsequent oxidation of1‐Me and1‐Et with pyridine‐ N ‐oxide (1 equiv) gave anionic η 2 ‐silaaldehydetungsten complexes [(η 5 ‐C5 Me4 R)(CO)2 W{η 2 ‐OSiH(Tsi)}][H Me I i Pr] (R=Me (2‐Me ); R=Et (2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis.