Reactions of LiE(SiMe3)3, E = Si, Ge:: X-ray crystal structure of the cyclotetrastannane [ClSnSi(SiMe3)3]4
Reactions of LiE(SiMe3)3, E = Si, Ge:: X-ray crystal structure of the cyclotetrastannane [ClSnSi(SiMe3)3]4
复制标题
DOI：
10.1021/ic9900455
复制
发表时间：
1999-06-14
影响因子：
4.6
通讯作者：
Geanangel, RA
中科院分区：
文献类型：
--
作者：
Mallela, SP;Saar, Y;Geanangel, RA
SnCl2的反应。二氧六环与2当量的Li(THF)(3)Si(SiMe3)(3)在正己烷中反应，以合理的产率得到环四锡[(Me3Si)(3)SiSnCl4](4)。从正戊烷出发，产物在P(1)的棒状空间群(三斜晶系)上结晶为红色橙色分解物，a=14.735(2)埃，b=14.976(2)埃，c=24.066(3)埃，α=76.94度，β=76.19度，伽马=62.11度，V=4517.5埃(3)，Z=2。锡-锡环由一个略微扭曲的非平面矩形组成，其距离为2.8054(6)。2.8111(6)、2.9122(6)和2.9146(6)埃。戊烷分子是无序的。用1当量的Li(THF)3Si(SiMe_3)_3或Li(THF)(2.5)Ge(SiMe_3)(3)处理所选择的单卤族和双卤族锗，得到(Me3Si)(3)EGe(CF3)(3)(E=Si，Ge)和(Me3Si)(3)GeR3(R=Cl，CH3，C6H5)。除单取代产物外，GeCl4与1当量的Li(THF)(2.5)Ge(SiMe3)3反应还得到少量的线型四锗(Me3Si)(3)GeGeCl2GeCl2Ge(SiMe3)(3)。类似苯基衍生物(Me3Si)(3)GeGePh2GePh2Ge(SiMe3)(3)用2当量的锗锂试剂处理Ph2GeCl2，得到了较好的产率。
Reaction of SnCl2. dioxane with 2 equiv of Li(THF)(3)Si(SiMe3)(3) in hexane afforded the cyclotetrastannane [(Me3Si)(3)SiSnCl](4) in reasonable yield. From pentane, the product crystallized as a red-orange disolvate in the P (1) over bar space group (triclinic) with a = 14.735(2) Angstrom, b = 14.976(2) Angstrom, c = 24.066(3) Angstrom, alpha = 76.94 degrees, beta = 76.19 degrees, gamma = 62.11 degrees, V = 4517.5 Angstrom(3), and Z = 2. The Sn-4 ring consisted of a slightly distorted, nonplanar (fold angle = 18.9 degrees) rectangle with Sn-Sn distances of 2.8054(6), 2.8111(6), 2.9122(6), and 2.9146(6) Angstrom. The pentane molecules were disordered. Selected mono- and dihalogermanes were treated with 1 equiv of Li(THF)3Si(SiMe3)3 or Li(THF)(2.5)Ge(SiMe3)(3), affording (Me3Si)(3)EGe(CF3)(3) (E = Si, Ge) and (Me3Si)(3)GeGeR3 (R = Cl, CH3, C6H5). Besides the monosubstitution product, the reaction of GeCl4 with 1 equiv of Li(THF)(2.5)Ge(SiMe3)3 also gave a small amount of the linear tetragermane (Me3Si)(3)GeGeCl2GeCl2Ge(SiMe3)(3). Good yields of the analogous phenyl derivative, (Me3Si)(3)GeGePh2GePh2Ge(SiMe3)(3), were obtained by treating Ph2GeCl2 with 2 equiv of the lithium-germyl reagent.