The reaction of BX₃ (X = Cl, Br, I) with SbR₃ (R = Et,ⁱPr) in anhydrous hexane or toluene produced moisture-sensitive [BX₃(SbR₃)], whose stability increases with halide: Cl < Br < I. Unstable [BF₃(SbR₃)] species were also characterized spectroscopically but lose BF₃ very readily. The [MX₃(SbR₃)] (M = Al, Ga, In) complexes were isolated from hexane solution; the Ga and In complexes can be recrystallized unchanged from CH₂Cl₂, but [AlX′₃(SbR₃)] (X′ = Br, I) undergoes X′/Cl exchange with the solvent. The new complexes were characterized by IR and multinuclear NMR spectroscopy (¹H, ¹³C{¹H}, ¹¹B, ²⁷Al, ⁷¹Ga, ¹¹⁵In, as appropriate). X-ray crystal structures are reported for [BX₃(SbR₃)] (X = Br, I; R = Et, ⁱPr; X = Cl, R = ⁱPr), [AlI₃(SbⁱPr₃)], [GaX₃(SbR₃)] (X = Cl, I; R = ⁱPr), [GaBr₃(SbEt₃)], and [InX₃(SbR₃)] (X = Cl, I; R = Et, ⁱPr); all contain pseudotetrahedral geometries at both the group 13 and antimony atoms, and comparisons with phosphine and arsine analogues are discussed. The donor–acceptor bond lengths are unexceptional, but coordination of the stibine is accompanied by a significant widening of the C–Sb–C angles and a small reduction in C–Sb distances. DFT calculations confirm these results from significant changes in the antimony 5s and 5p contributions to the Sb–C bonds, with corresponding increases in the 5p character of the antimony-based “lone pair” on coordination. Intermolecular hypervalent Cl···Sb interactions are present in the two [InCl₃(SbR₃)] complexes but absent in the others.

中文翻译：

---

硼，铝，镓和三卤化铟的三烷基sti络合物：合成，性质和键合

BX ₃（X = Cl，Br，I）与SbR ₃（R = Et，ⁱ Pr）在无水己烷或甲苯中的反应产生对水分敏感的[BX ₃（SbR ₃）]，其稳定性随卤化物：Cl的增加而增加还通过光谱表征了不稳定的[BF ₃（SbR ₃）]种类，但很容易损失BF ₃。从己烷溶液中分离出[MX ₃（SbR ₃）]（M = Al，Ga，In）配合物。的Ga和In复合物可以从CH重结晶不变₂氯₂，但[ALX' ₃（SBR ₃）]（X'= Br，I）与溶剂进行X'/ Cl交换。通过IR和多核NMR光谱法（适当地，¹ H，¹³ C { ¹ H}，¹¹ B，²⁷ Al，⁷¹ Ga，¹¹⁵ In）表征新的配合物。报告了[BX ₃（SbR ₃）]的X射线晶体结构（X = Br，I; R = Et，ⁱ Pr; X = Cl，R = ⁱ Pr），[AlI ₃（Sb ⁱ Pr ₃）] ，[GaX ₃（SbR ₃）]（X = Cl，I; R = ⁱ Pr），[GaBr ₃（SbEt ₃）]和[InX ₃（SbR ₃）]（X = Cl，I; R = Et，ⁱ Pr）; 它们都在第13组和锑原子上都包含伪四面体几何形状，并讨论了与膦和砷化氢类似物的比较。供体-受体键的长度无异常，但斯蒂宾因的配位伴随着C–Sb–C角的显着加宽和C–Sb距离的小幅减小。DFT计算证实了这些结果是由于锑中5s和5p对Sb-C键的贡献发生了显着变化，以及基于锑的“孤对”配位过程中5p特性的相应增加。两种[InCl ₃（SbR ₃）]复合体，而其他复合体则不存在。