Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 30, Pages 8746-8750Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201503455
Keywords
carbon monoxide; CC coupling; ketenylidenes; reduction; silylene complexes
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Funding
- Deutsche Forschungsgemeinschaft [DFG SCHE 906/5-1]
- Alfried Krupp Foundation
- Scientific and Technical Research Council of Turkey [TUBITAK-2214A]
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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 Group6 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.
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