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Stabilization of a Silaaldehyde by its η 2 Coordination to Tungsten
Author(s) -
Fukuda Tetsuya,
Hashimoto Hisako,
Sakaki Shigeyoshi,
Tobita Hiromi
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201507956
Subject(s) - silylene , chemistry , pyridine , deprotonation , carbene , crystal structure , tungsten , medicinal chemistry , ring (chemistry) , stereochemistry , crystallography , catalysis , ion , organic chemistry , silicon
Treatment of pyridine‐stabilized silylene complexes [(η 5 ‐C 5 Me 4 R)(CO) 2 (H)WSiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe 3 ) 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 ‐C 5 Me 4 R)(CO) 2 WSiH(Tsi)][H Me I i Pr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐ N ‐oxide (1 equiv) gave anionic η 2 ‐silaaldehydetungsten complexes [(η 5 ‐C 5 Me 4 R)(CO) 2 W{η 2 ‐OSiH(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.