Activation of CO Using a 1,2‐Disilylene: Facile Synthesis of an Abnormal N‐Heterocyclic Silylene
Palak Garg, Ambre Carpentier, Iskander Douair, Deepak Dange, Yixiao Jiang, K. Yuvaraj, Laurent Maron, Cameron Jones
Abstract
Abstract Reaction of the 1,2‐disilylene, [{ArC(NDip) 2 }Si] 2 1 (Dip=2,6‐diisopropylphenyl, Ar=4‐C 6 H 4 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 ( a NHC), 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 (κ 2 ‐Si,Si‐ 2 )] 3 , while reaction with [Fe(CO) 5 ] gives the unusual silyleneyl bridged complex, [{Fe 2 (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 a NHCs, d‐block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.