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Reaction of 1,1‐Dimethylsilene with Formaldehyde
Author(s) -
Trommer Martin,
Sander Wolfram,
Ottosson CarlHenrik,
Cremer Dieter
Publication year - 1995
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199509291
Subject(s) - diradical , formaldehyde , singlet state , carbene , photochemistry , chemistry , silylation , aldehyde , silence , van der waals force , medicinal chemistry , computational chemistry , organic chemistry , catalysis , molecule , physics , atomic physics , excited state , acoustics
Even at 30 K 1,1‐dimethylsilene ( 1 ) reacts smoothly with formaldehyde in a thermal transformation to give trimethylsiloxycarbene ( 2 ). This singlet carbene is extremely photolabile and rapidly rearranges on irradiation with visible light (λ > 570 nm) in a 1,2 migration of the silyl group to give aldehyde 3 . According to CCSD(T)/6‐31G(d,p) calculations on the parent silence, reaction takes place via a van der Waals complex and a diradical intermediate.