Activation of CO Using a 1,2-Disilylene: Facile Synthesis of an Abnormal N-Heterocyclic Silylene

Reaction of the 1,2-disilylene, [{ArC(NDip)₂ }Si]₂ 1 (Dip=2,6-diisopropylphenyl, Ar=4-C₆ H₄ Bu^t ), with CO proceeds via insertion of CO into one Si-N bond, and Si-Si bond cleavage, to cleanly give the bis(silylene), {ArC(NDip)₂ }Si(:)O $$ Ar 2, under ambient conditions. The reaction can be partially reversed when solutions of 2 are subjected to UV irradiation. The five-membered heterocyclic fragment of 2 represents the first silicon analogue of an "abnormal" N-heterocyclic carbene (aNHC), a view which is substantiated by a computational analysis of the compound. Reaction of 2 with [Mo(CO)₆ ] under UV light affords the chelate complex, [Mo(CO)₄ (κ² -Si,Si-2)] 3, while reaction with [Fe(CO)₅ ] gives the unusual silyleneyl bridged complex, [{Fe₂ (CO)₆ }{μ-Si[(NDip)₂ CAr]}₂ ] 4. The same coordination complexes can be accessed by reaction of 1 with [Mo(CO)₆ ] or [Fe(CO)₅ ] under UV light. As is the case for aNHCs, d-block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.