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Reductive Cleavage of Carbon Monoxide by a Disilenide
Author(s) -
Majumdar Moumita,
Omlor Isabell,
Yildiz Cem B.,
Azizoglu Akin,
Huch Volker,
Scheschkewitz David
Publication year - 2015
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.201503455
Subject(s) - carbon monoxide , chemistry , alkyne , silylene , dimer , reductive elimination , cleavage (geology) , triple bond , photochemistry , bond cleavage , polymer chemistry , organic chemistry , catalysis , double bond , materials science , silicon , fracture (geology) , composite material
The complete reductive cleavage of the triple bond in carbon monoxide was achieved using a lithium disilenide at room temperature. The CC‐coupled product can be regarded as a silanone dimer with pending alkyne and silirene moieties and incorporates two equivalents of CO per disilenide unit. A formation mechanism via ketenyl intermediates is proposed on the basis of DFT calculations and elucidated experimentally by employing Group 6 metal carbonyls as both stabilizing entity and source of CO in the reaction with disilenide. The isolation of cyclic silylene complexes with weakly donating ketenyl donor groups further supports the mechanistic scenario.