Activation of CO Using a 1, 2‐Disilylene: Facile Synthesis of an Abnormal N‐Heterocyclic Silylene. (14th March 2022)

• Record Type: Journal Article
• Authors: Garg, Palak; Carpentier, Ambre; Douair, Iskander; Dange, Deepak; Jiang, Yixiao; Yuvaraj, K.; Maron, Laurent; Jones, Cameron
• Is Part Of: Angewandte Chemie. Volume 134:Number 20(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-14
• Subjects: 1, 2-Disilylene -- Abnormal N-Heterocyclic Carbenes -- Bis(Silylene) -- Carbon Monoxide -- Small Molecule Activation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202201705
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 C S i ( : ) ( N D i p )​ 2 C ‾ 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, [{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 a NHCs, d‐block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations. Abstract : Reaction of a 1, 2‐disilylene with CO under ambient conditions leads to a bis(silylene), the five‐membered heterocycle of which represents the first silicon analogue of an "abnormal" N‐heterocyclic carbene (see picture). Reactions of the bis(silylene) with transition metal carbonyls lead to different outcomes, including a chelate complex of the Mo(CO)4 fragment.