Departamento de Química, Universidad de la Rioja, Grupo de Síntesis Química de La Rioja UA-CSIC Complejo Cientifico Tecnológico, 26004 Logroño, Spain.
Inorg Chem. 2010 Jun 21;49(12):5530-41. doi: 10.1021/ic1003484.
The reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with SbMes(n)Ph(3-n) (n = 3 (1), 2 (2), 1 (3)) produces the 1:1 adducts [AuCl(SbMes(n)Ph(3-n))] (n = 3 (4), 2 (5), 1 (6)), with a Sb-Au-Cl environment, regardless of the molar ratio used (1:1 to 1:4). Addition of the same stibines to [Au(tht)(2)]ClO(4) (molar ratio 1:1 to 1:4) results in isolation of the 1:2 adducts [Au(SbMes(n)Ph(3-n))(2)]ClO(4) (n = 3 (7), 2 (10)), containing linear Sb-Au-Sb fragments, or the 1:3 adduct [Au(SbMesPh(2))(3)]ClO(4) (11), with a quasi trigonal planar AuSb(3) core. The same 1:2 cations are produced when [Au(tht)(2)]CF(3)SO(3) is reacted with 1 or following a rearrangement process when 4 is treated with AgSbF(6), that is, [Au(SbMes(3))(2)]X (X = CF(3)SO(3) (8), SbF(6) (9)). The compounds were characterized by spectroscopic methods, and the molecular structures of 2-4, 7, 8.2CDCl(3), 9, and 11 were established by single-crystal X-ray diffraction. Theoretical calculations were carried out on model systems of type ER(3) and Au(ER(3))(n) (E = P or Sb; R = Ph or Mes; n = 2, 3, or 4) to gain insight into the bonding nature of SbR(3) ligands in homoleptic gold-stibine adducts, in comparison with phosphine-gold(I) compounds. Steric effects govern the coordination of stibines with mesityl substituents. A preference for higher coordination numbers is observed for SbPh(3) when compared with PPh(3) and experimentally observed C-Sb-C and Sb-C structural distortions of stibines upon coordination are reproduced theoretically.
[AuCl(tht)]（tht=四氢噻吩）与 SbMes(n)Ph(3-n)（n=3（1）、2（2）、1（3））反应生成 1:1 加合物[AuCl(SbMes(n)Ph(3-n))]（n=3（4）、2（5）、1（6）），具有 Sb-Au-Cl 环境，无论使用的摩尔比如何（1:1 至 1:4）。将相同的锑化合物添加到[Au(tht)(2)]ClO(4)（摩尔比 1:1 至 1:4）中，可分离出 1:2 加合物[Au(SbMes(n)Ph(3-n))(2)]ClO(4)（n=3（7）、2（10）），含有线性 Sb-Au-Sb 片段，或 1:3 加合物[Au(SbMesPh(2))(3)]ClO(4)（11），具有准三角平面 AuSb(3)核。当[Au(tht)(2)]CF(3)SO(3)与 1 反应或 4 用 AgSbF(6)处理时发生重排过程，也会生成相同的 1:2 阳离子，即[Au(SbMes(3))(2)]X（X=CF(3)SO(3（8）、SbF(6)（9）））。通过光谱方法对化合物进行了表征，并通过单晶 X 射线衍射确定了 2-4、7、8.2CDCl(3)、9 和 11 的分子结构。还对 ER(3)和[Au(ER(3))(n)]+(E=P 或 Sb；R=Ph 或 Mes；n=2、3 或 4) 型模型体系进行了理论计算，以深入了解同核金-锑化物加合物中 SbR(3)配体的键合性质，并与膦-金（I）化合物进行了比较。空间位阻效应控制着带有均三甲苯基取代基的锑化物的配位。与 PPh(3)相比，观察到 SbPh(3)具有更高的配位数偏好，并且理论上再现了配位时锑化物的 C-Sb-C 和 Sb-C 结构扭曲。
