French Family Science Center, Duke University, Durham, NC 27708-0346 (USA).
Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6867-9. doi: 10.1002/anie.201501474. Epub 2015 Apr 23.
Hydride abstraction from the gold (disilyl)ethylacetylide complex [(P)Au{η(1) -C≡CSi(Me)2CH2CH2SiMe2H}] (P=P(tBu)2o-biphenyl) with triphenylcarbenium tetrakis(pentafluorophenyl)borate at -20 °C formed the cationic gold (β,β-disilyl)vinylidene complex (P)Au=C=CSi(Me)2CH2CH2Si(Me)2B(C6F5)4(-) with ≥90% selectivity. (29)Si NMR analysis of this complex pointed to delocalization of positive charge onto both the β-silyl groups and the (P)Au fragment. The C1 and C2 carbon atoms of the vinylidene complex underwent facile interconversion (ΔG(≠)=9.7 kcal mol(-1)), presumably via the gold π-disilacyclohexyne intermediate (P)Au{η(2)-C≡CSi(Me)2CH2CH2Si(Me)2}B(C6F5)4(-).
与三苯基碳鎓四（五氟苯基）硼酸盐在-20°C条件下，从金（二硅乙基乙酰基）炔配合物[(P)Au{η(1)-C≡CSi(Me)2CH2CH2SiMe2H}]（P=P(tBu)2o-联苯）中抽取出氢化物，形成了阳离子金（β,β-二硅基）亚乙烯基配合物(P)Au=C=CSi(Me)2CH2CH2Si(Me)2B(C6F5)4(-)，其选择性大于 90%。对该配合物的(29)Si NMR 分析表明正电荷局域在β-硅基和（P）Au 片段上。亚乙烯基配合物的 C1 和 C2 碳原子易于相互转化（ΔG(≠)=9.7 kcal mol(-1)），可能通过金π-二硅环辛炔中间体(P)Au{η(2)-C≡CSi(Me)2CH2CH2Si(Me)2}B(C6F5)4(-)进行。
