Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ-532 10, Pardubice, Czech Republic.
Dalton Trans. 2013 Jun 7;42(21):7660-71. doi: 10.1039/c3dt50278c.
The reactivity of (L(CN))(2)Sn (1) (where L(CN) is 2-(N,N-dimethylaminomethyl)phenyl-) towards various substrates containing E–Cl bond(s) has been studied (E = C, Si, Ge and Sn). Alkyl chlorides like chloroform or dichloromethane reacts with 1 to form (L(CN))(2)SnCl(2) and unidentified by-products in poor yields. The reaction of benzoyl chloride with 1 at low temperature yielded a thermally unstable product (L(CN))(2)Sn(Cl)C(O)Ph (2) which was isolated and characterized by both multinuclear NMR spectroscopy and X-ray diffraction techniques. The vicinity of the central tin atom in 2 reveals trigonal bipyramidal geometry. Attempts to oxidize 2 by dioxygen to give the corresponding organotin(IV) benzoate failed. On the other hand, the reaction of the in situ prepared (L(CN))(2)Sn=O (synthesized by the reaction of 1 with dioxygen) with PhCOCl resulted in the formation of the desired organotin(IV) benzoate (L(CN))(2)Sn(Cl)C(=O)OPh (3). The reaction of 1 with Ph3GeCl yielded triphenylgermyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)GePh(3) (4) which subsequently gave mixed diorganotin(IV) chloride-oxide (L(CN))(2)SnClO (5) upon loss of the GePh(3) moiety in the air. When the same reaction was carried out in benzene instead of chloroform a unique Ph(3)Ge[Sn(6)O(8)] cluster (6) was obtained. Similarly, the reaction of 1 with Ph3SiCl provided triphenylsilyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)SiPh(3) (7) which was then oxidized to (L(CN))(2)Sn(Cl)OSiPh(3) (8). The unprecedented reaction of 1 with (n-Bu)(3)SnCl provided the distannane (L(CN))(2)Sn(Cl)SnBu(3) (9) which could be oxidized by dioxygen to a distannoxane (L(CN))(2)Sn(Cl)OSnBu(3) (10). In addition, the solid-state structures of 3, 5, 6 and 8 were determined by the X-ray diffraction techniques.
（L(CN))(2)Sn（1）（其中 L(CN) 是 2-(N,N-二甲基氨甲基)苯基）对含有 E-Cl 键的各种底物的反应性进行了研究（E=C、Si、Ge 和 Sn）。氯仿或二氯甲烷等烷基氯化物与 1 反应生成（L(CN))(2)SnCl(2)和产率低的未知副产物。在低温下，苯甲酰氯与 1 反应生成热不稳定的产物（L(CN))(2)Sn(Cl)C(O)Ph（2），通过多核 NMR 光谱和 X 射线衍射技术对其进行了分离和表征。2 中中心锡原子的临近区域呈现三角双锥几何形状。尝试用氧气将 2 氧化为相应的有机锡（IV）苯甲酸盐，但未能成功。另一方面，（L(CN))(2)Sn=O（通过 1 与氧气反应合成）与 PhCOCl 的原位反应导致形成所需的有机锡（IV）苯甲酸盐（L(CN))(2)Sn(Cl)C(=O)OPh（3）。1 与 Ph3GeCl 的反应生成三苯基取代的二有机锡（IV）氯化物（L(CN))(2)Sn(Cl)GePh(3)（4），随后在空气中失去 GePh(3)部分后生成混合二有机锡（IV）氯化物-氧化物(L(CN))(2)SnClO（5）。当在苯中而不是氯仿中进行相同的反应时，得到了独特的Ph(3)Ge[Sn(6)O(8)]簇（6）。同样，1 与 Ph3SiCl 的反应提供了三苯基取代的二有机锡（IV）氯化物（L(CN))(2)Sn(Cl)SiPh(3)（7），然后将其氧化为（L(CN))(2)Sn(Cl)OSiPh(3)（8）。1 与（n-Bu)(3)SnCl 的前所未有的反应提供了二锡烷（L(CN))(2)Sn(Cl)SnBu(3)（9），它可以被氧气氧化为二锡烷氧化物（L(CN))(2)Sn(Cl)OSnBu(3)（10）。此外，通过 X 射线衍射技术确定了 3、5、6 和 8 的固体结构。
