Faculty of Chemistry, Inorganic Chemistry, and Center for Nanointegration Duisburg-Essen (CENIDE) , University of Duisburg-Essen , Universitätsstrasse 7 , 45141 Essen , Germany.
Institute for Inorganic Chemistry and Structural Chemistry , University of Düsseldorf , 40225 Düsseldorf , Germany.
Inorg Chem. 2018 Aug 6;57(15):9495-9503. doi: 10.1021/acs.inorgchem.8b01489. Epub 2018 Jul 24.
LGa {L = HC[C(Me)N(2,6- iPrCH)]} reversibly reacts with EPh (E = Sb, Bi) in a temperature-dependent equilibrium reaction with insertion into the E-E bond and formation of LGa(EPh) (E = Sb 1, Bi 2). Analogous findings were observed in the reactions of LGa {L = (CH)NC[N(2,6- iPrCH)]} with ER (R = Ph, Et), yielding LGa(EPh) (E = Sb 3, Bi 4) and LGa(EEt) (E = Sb 5, Bi 6). 1-3 and 5 were isolated by fractional crystallization at low temperature, whereas 4 and 6 could not be isolated in their pure form even at low temperature. In contrast, reactions of [CpAl] (Cp = CMe) with SbR (R = Ph, Et) and BiEt did not proceed with insertion into the E-E bonds but with formation of (CpAl)E (E = Sb, 7; Bi, 8), whereas the reaction with BiPh yielded metallic bismuth. 8 was also formed in the reaction of [CpAl] and BiEt at ambient temperature, whereas the analogous reaction of [CpAl] with SbEt did not yield 7 even under drastic reaction conditions (120 °C, 3 days). In contrast, CpGa and SbR (R = Ph, Et) were found to react only at elevated temperature (120 °C) with formation of antimony metal.
LGa {L = HC[C(Me)N(2,6- iPrCH)]} 与 EPh（E = Sb，Bi）在温度依赖的平衡反应中可逆反应，插入 E-E 键并形成 LGa(EPh)（E = Sb 1，Bi 2）。在 LGa {L = (CH)NC[N(2,6- iPrCH)]} 与 ER（R = Ph，Et）的反应中也观察到类似的发现，生成 LGa(EPh)（E = Sb 3，Bi 4）和 LGa(EEt)（E = Sb 5，Bi 6）。1-3 和 5 通过低温分步结晶分离，而 4 和 6 即使在低温下也不能以纯形式分离。相比之下，[CpAl]（Cp = CMe）与 SbR（R = Ph，Et）和 BiEt 的反应不会插入 E-E 键，而是形成 (CpAl)E（E = Sb，7；Bi，8），而与 BiPh 的反应则生成金属铋。8 也在 [CpAl] 和 BiEt 的反应中形成，而在相同条件下，[CpAl] 与 SbEt 的反应甚至在剧烈的反应条件下（120°C，3 天）也不会生成 7。相比之下，CpGa 和 SbR（R = Ph，Et）仅在高温（120°C）下反应，形成锑金属。
