On the Mechanism of the Disproportionation of Chlorinated Silanes under the Influence of Lewis Bases

The first N-heterocyclic carbene adducts of arylchlorosilylenes are reported and compared with the homologous germanium compounds. The arylsilicon(II) chlorides SiArCl(Im-Me(4)) [Ar=C(6)H(3)-2,6-Mes(2) (Mes=C(6)H(2)-2,4,6-Me(3)), C(6)H(3)-2,6-Trip(2) (Trip=C(6)H(2)-2,4,6-iPr(3))] were obtained selectively on dehydrochlorination of the arylchlorosilanes SiArHCl(2) with 1,3,4,5-tetramethylimidazol-2-ylidene (Im-Me(4)). The analogous arylgermanium(II) chlorides GeArCl(Im-Me(4)) were prepared by metathetical exchange of GeCl(2)(Im-Me(4)) with LiC(6)H(3)-2,6-Mes(2) or addition of Im-Me(4) to GeCl(C(6)H(3)-2,6-Trip(2)). All compounds were fully characterized. Density functional calculations on ECl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)), where E=Si, Ge, at different levels of theory show very good agreement between calculated and experimental bonding parameters, and NBO analyses reveal similar electronic structures of the two aryltetrel(II) chlorides. The low gas-phase Gibbs free energy of bond dissociation of SiCl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)) (Delta(calcd) degrees=28.1 kJ mol(-1)) suggests that the carbene adducts SiArCl(Im-Me(4)) may be valuable transfer reagents of the arylsilicon(II) chlorides SiArCl.

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On the Mechanism of the Disproportionation of Chlorinated Silanes under the Influence of Lewis Bases

Cited by 14 publications

References 21 publications

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Stable N‐Heterocyclic Carbene Adducts of Arylchlorosilylenes and Their Germanium Homologues

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