Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding
Trialkylstibine Complexes of Boron, Aluminum, Gallium, and Indium Trihalides: Synthesis, Properties, and Bonding
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DOI：
10.1021/acs.organomet.8b00265
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发表时间：
2018-07-09
期刊：
影响因子：
2.8
通讯作者：
Reid, Gillian
中科院分区：
文献类型：
--
作者：
Greenacre, Victoria K.;Levason, William;Reid, Gillian
BX_3（X = Cl，Br，I）与SbR_3（R = Et，Pr ~（-1））在无水己烷或甲苯中反应生成湿敏[BX_3（SbR_3）]，其稳定性随卤素：Cl < Br < I而增加。不稳定的[BF 3（SbR 3）]物种也进行了光谱表征，但很容易失去BF 3。[MX_3（SbR_3）]（M = Al，Ga，In）配合物可在CH_2Cl_2中重结晶，而[Al_X ′（3）（SbR_3）]（X ′ = Br，I）与溶剂发生X ′/Cl交换。通过红外光谱和多核核磁共振谱（H-1，C-13{H-1}，B-11，Al-27，Ga-71，In-115，视情况而定）对新配合物进行了表征。报道了[BX_3（SbR_3）]的X射线晶体结构（X = Br，I; R = Et，Pr1; X = Cl，R = Pr1），[AlI3（（SbPr3）-Pr1）]，[GaX3（SbR3）]（X = Cl、I; R = Pr-1）、[GaBr 3（SbEt3）]和[InX 3（SbR3）]（X = Cl，I; R = Et，Pr-1）;所有包含pseudotetrahedral几何形状在两个组13和锑原子，并与膦和胂类似物的比较进行了讨论。的donoracceptor键的长度是不例外的，但协调的锑化氢是伴随着一个显着扩大的CSbC角和一个小的减少CSb的距离。DFT计算证实了这些结果从锑5s和5 p贡献的SbC键的显着变化，与相应的增加，在5 p字符的锑为基础的“孤对”的协调。两个[InCl_3（SbR_3）]配合物中存在分子间超价Cl - Sb相互作用，而其它配合物中不存在。
The reaction of BX3 (X = Cl, Br, I) with SbR3 (R = Et,Pr-i) 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 (H-1, C-13{H-1}, B-11, Al-27, Ga-71, In-115, as appropriate). X-ray crystal structures are reported for [BX3(SbR3)] (X = Br, I; R = Et, Pr-i; X = Cl, R = Pr-i),[AlI3((SbPr3)-Pr-i)], [GaX3(SbR3)] (X = Cl, I; R = Pr-i), [GaBr3(SbEt3)], and [InX3(SbR3)] (X = Cl, I; R = Et, Pr-i); all contain pseudotetrahedral geometries at both the group 13 and antimony atoms, and comparisons with phosphine and arsine analogues are discussed. The donoracceptor bond lengths are unexceptional, but coordination of the stibine is accompanied by a significant widening of the CSbC angles and a small reduction in CSb distances. DFT calculations confirm these results from significant changes in the antimony 5s and 5p contributions to the SbC 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.