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The Singlet Excited State of a Stable Dialkylsilylene Is Responsible for Its Photoreactions
Author(s) -
Kira Mitsuo,
Ishida Shintaro,
Iwamoto Takeaki,
de Meijere Armin,
Fujitsuka Mamoru,
Ito Osamu
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200460317
Subject(s) - diradical , silylene , singlet state , chemistry , closure (psychology) , photochemistry , carbene , ring (chemistry) , triplet state , state (computer science) , excited state , computational chemistry , computer science , physics , organic chemistry , catalysis , molecule , atomic physics , silicon , political science , law , algorithm
The singlet 1,1‐diradical ( 1 B 1 ) state of a silylene plays a key role in its photoreactions with benzenes and alkenes, even though similar 1 B 1 states are rarely encountered in carbene chemistry. The photochemical addition to alkenes should be stepwise and the ring closure of the intermediate singlet 1,3‐diradicals was very facile with rates ( k c ) of more than 10 9 s −1 (see scheme).