Details

Autor(en) / Beteiligte

• Majumdar, Moumita
• Omlor, Isabell
• Yildiz, Cem B.
• Azizoglu, Akin
• Huch, Volker
• Scheschkewitz, David

Titel

Reductive Cleavage of Carbon Monoxide by a Disilenide

Ist Teil von

• Angewandte Chemie (International ed.), 2015-07, Vol.54 (30), p.8746-8750

Auflage

International ed. in English

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2015

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The complete reductive cleavage of the triple bond in carbon monoxide was achieved using a lithium disilenide at room temperature. The CC‐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. Hidden powers: Lithium disilenide reductively cleaves the strongest bond in chemistry, the CO bond of carbon monoxide, at room temperature. A key step in the Fischer–Tropsch process is reiterated by an anionic molecular main‐group system with SiSi bonds. The mechanism is elucidated by DFT calculations and model reactions with Group 6 hexacarbonyls.