Facile activation of inert small molecules using a 1, 2-disilylene. Issue 20 (10th May 2022)

• Record Type: Journal Article
• Authors: Garg, Palak; Dange, Deepak; Jiang, Yixiao; Jones, Cameron
• Is Part Of: Dalton transactions. Volume 51:Issue 20(2022)
• Page Start: 7838
• Page End: 7844
• Publication Date: 2022-05-10
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt00721e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A 1, 2-disilylene reductively activates a series of unsaturated small molecule substrates ( viz. Bu t NC:, C2 H4, CO2 and N2 O), yielding a range of novel compound types (see picture; Dip = 2, 6-diisopropylphenyl, Ar = 4-C6 H4 Bu t ). Abstract : Reactions of the known amidinate stabilised 1, 2-disilylene, [{ArC(NDip)2 }Si]2 1 (Dip = 2, 6-diisopropylphenyl, Ar = 4-C6 H4 Bu t ) with a series of inert, unsaturated small molecule substrates have been carried out. Compound 1 reduces Bu t NC: to give the singlet biradicaloid 1, 3-disilacyclobutanediyl [{ArC(NDip)2 }Si(μ-CNBu t )]2 3, which can be oxidised by 1, 2-dibromoethane to give [{ArC(NDip)2 }(Br)Si(μ-CNBu t )]2 4 . Disilylene 1 reduces two molecules of ethylene to give an unprecedented disilabicyclo[2.2.0]hexane, [{ArC(NDip)2 }Si(μ-C2 H4 )]2 5 . In contrast, only one molecule of ethylene inserts in the Ge–Ge bond of the digermylene analogue of 1, viz. [{ArC(NDip)2 }Ge]2 6, leading to the formation of the bis(germylene), [{ArC(NDip)2 }Ge]2 (μ-C2 H4 ) 7 . Compound 1 reduces CO2, generating CO, and the oxo/carbonate-bridged disilicon(iv ) system, {ArC(NDip)2 }Si(μ-CO3 )2 (μ-O)Si{(NDip)2 CAr} 10, while its reaction with N2 O proceeds via generation of N2, and a hydrogen abstraction process, to give the oxo/hydroxy disilicon(iv ) species, [{ArC(NDip)2 }(HO)Si(μ-O)]2 11 . This study highlights new small molecule activation chemistry for 1, 2-disilylenes, which could lead to further adoption of compound 1 as a potent reducing reagent for the transformation of inert unsaturated molecules into value added products.