Phosphorus Silicon Compounds from the Reduction of MesP(H)SiCl2Ph/Carbene with and without Metal

Abstract

MesP(H)SiCl2Ph (Mes = 2,4,6‐Me3C6H2) (7) with a reactive Si–Cl and P–H bond can easily be reduced by KC8 or alternatively by a carbene to give remarkable phosphorus silicon compounds. 7 is readily synthesized from the reaction of MesPH2 sequentially with nBuLi and PhSiCl3 in a 1:1:1 ratio. KC8 reduction of MesP(H)SiCl2Ph (7) in the presence of cyclic alkyl(amino) carbene (cAACMe) gives (MesPH)3SiPh (8) and cAAC‐stabilized Si2Ph2 (9). In addition, 9 might also be formed by the reduction of PhSiCl3 using KC8 in the presence of cAACMe. Treatment of MesP(H)SiCl2Ph (7) with IiPr2Me2 (IiPr2Me2 = 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) in a molar ratio of 1:2 results in HCl elimination as IiPr2Me2·HCl. The second equivalent of IiPr2Me2 was used to yield well‐defined phosphasilene (10) containing a Ph(Cl)Si=PMes moiety. This unit will gain much application in ligand design because the chlorine atom can readily be replaced by other substituents.

(MesPH)3SiPh (8) together with cyclic alkyl(amino) carbene (cAACMe)‐stabilized Si2Ph2 (9) have been obtained from the reduction of MesP(H)SiPhCl2 (7) with KC8 in the presence of cAACMe. Treatment of MesP(H)SiPhCl2 with IiPr2Me2 {IiPr2Me2 = [(Me)CN(iPr)]2C:} in a molar ratio of 1:2 resulted in HCl elimination as IiPr2Me2·HCl and coordination of the second equivalent IiPr2Me2 to give a well‐defined phosphasilene (10) containing a Ph(Cl)Si=PMes moiety. image John Wiley \u0026 Sons, Ltd.