Phosphanylhydrosilylalkynes R₂HSiCCPAr₂ (R,Ar: Me,4‐tBuC₆H₄ 1, Me,Mes 2, Mes,Ph 3; Mes = 2,4,6‐Me₃C₆H₂) were prepared and the reactions with B(C₆F₅)₃ were studied. Reaction of 1 and B(C₆F₅)₃ produced E‐alkene {(E)‐(C₆F₅)₃BCHC[P(4‐tBuC₆H₄)₂]SiMe₂}₂ (4) and that of 2 and B(C₆F₅)₃ yielded Z‐alkene (Z)‐(C₆F₅)₂BCHC(PMes₂)SiMe₂(C₆F₅) (5). The former is proposed to go through a key [Me₂HSi]⁺ for function while the latter via the phosphacyclopropene intermediate, both of which are a result by self‐hydrosilylation. Reaction of 3 and B(C₆F₅)₃ generated at room temperature a P→B coordination compound Mes₂HSiCCP(Ph₂)B(C₆F₅)₃ (6) and at 100 °C the 1,1‐carboboration E‐alkene (E)‐Mes₂HSi(Ph₂P)CC(C₆F₅)B(C₆F₅)₂ (7). Kinetic study and DFT calculations were accomplished for reaction of 2 and B(C₆F₅)₃ to 5. The mechanisms of these reactions have been discussed. The reactions of the P/Si⁺ LPs Me₂Si(Ph₂P)CCHB(C₆F₅)₃}₂ (3a) and 4 were also investigated. Compound 4 disassociated H₂O into {(E)‐(C₆F₅)₃BCHC[PH‐4‐tBuC₆H₄)₂]Si(Me₂)}₂(µ‐O) (8) and (E)‐(C₆F₅)₃BCHC[PH(4‐tBu‐C₆H₄)₂]Si(Me₂)O(HNC₅H₅) (9). Compound 3a reacted with tBuNCO by [3+2] dipolar cycloaddition to give a C₂OPSi‐heterocycle [(C₆F₅)₃BHC]CSi(Me₂)P(Ph₂)OC(NtBu) (10). Furthermore, 4 reacted with tBuNCO and then H₂O to afford (E)‐(F₅C₆)₃BHCC[P(4‐tBuC₆H₄)₂C(O)NHtBu][Si(Me₂)OH(NC₅H₅)] (11) through a C₂OPSi‐heterocycle intermediate followed by the H₂O‐disassociation under the C₂OPSi‐ring opening.

中文翻译：

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膦酰基氢甲硅烷基炔与B（C6F5）3的多功能反应模式：显着的基团取代作用。

制备了膦酰基氢硅烷基炔烃R ₂ HSiCCPAr ₂（R，Ar：Me，4- t BuC ₆ H ₄ 1，Me，Mes 2，Mes，Ph 3 ; Mes = 2,4,6-Me ₃ C ₆ H ₂），研究了与B（C ₆ F ₅）_3的反应。的反应1和B（C ₆ ˚F ₅）₃产生È -烯烃{（ë（C - ）₆ ˚F ₅）₃ BCHC [P（4-吨BUC₆ ħ ₄）₂ ]森达₂ } ₂（4）和的2和B（C ₆ ˚F ₅）₃，得到Ž -烯烃（Ž） - （C ₆ ˚F ₅）₂ BCHC（机动设备₂）森达₂（C ₆ F ₅）（5）。建议前者通过密钥[Me ₂ HSi] ⁺后者通过磷环丙烯中间体发挥作用，两者都是自氢硅烷化的结果。的反应3和B（C ₆ ˚F ₅）₃在室温下为P→乙配位化合物生成的Mes ₂ HSiCCP（PH ₂）B（C ₆ ˚F ₅）₃（6），并在100℃下的1,1-二碳硼化E-烯烃（E）-Mes ₂ HSi（Ph ₂ P）CC（C ₆ F ₅）B（C ₆ F ₅）₂（7）。对2和B（C ₆ F ₅）₃至5的反应进行了动力学研究和DFT计算。已经讨论了这些反应的机理。还研究了P / Si ⁺ LPs Me ₂ Si（Ph ₂ P）CCHB（C ₆ F ₅）₃ } ₂（3a）和4的反应。化合物4将H ₂ O分解为{（E）‐（C ₆ F ₅）₃ BCHC [PH‐4‐ t BuC₆ H ₄）₂ ] Si（Me ₂）} ₂（µ- O）（8）和（E）-（C ₆ F ₅）₃ BCHC [PH（4 - t Bu‐C ₆ H ₄）₂ ] Si （Me ₂）O（HNC ₅ H ₅）（9）。化合物3a通过[3 + 2]偶极环加成与t BuNCO反应，得到C ₂ OPSi-杂环[（C ₆ F ₅）₃ BHC] CSi（Me ₂）P（Ph ₂）OC（N t Bu）（10）。此外，4与t BuNCO反应，然后与H ₂ O反应，得到（E）-（F ₅ C ₆）₃ BHCC [P（4- t BuC ₆ H ₄）₂ C（O）NH t Bu] [Si（Me ₂）OH（NC ₅ H ₅）]（11）通过C ₂ OPSi杂环中间体，然后在C ₂ OPSi环开口下进行H ₂ O分解。