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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Activation of E-Cl bonds (E = C, Si, Ge and Sn) by a C,N-chelated stannylene
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Activation of E-Cl bonds (E = C, Si, Ge and Sn) by a C,N-chelated stannylene

机译：C，N螯合的亚锡激活E-Cl键（E = C，Si，Ge和Sn）

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摘要

The reactivity of (L~CN))_2Sn (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))_2SnCl_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))_2Sn(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))_2SnO (synthesized by the reaction of 1 with dioxygen) with PhCOCl resulted in the formation of the desired organotin(iv) benzoate (L~CN))_2Sn(Cl)C(O)OPh (3). The reaction of 1 with Ph_3GeCl yielded triphenylgermyl-substituted diorganotin(iv) chloride (L~CN))_2Sn(Cl)GePh_3 (4) which subsequently gave mixed diorganotin(iv) chloride-oxide [(L~(CN))_2SnCl]_2O (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_3Ge]_4[Sn_6O_8] cluster (6) was obtained. Similarly, the reaction of 1 with Ph_3SiCl provided triphenylsilyl-substituted diorganotin(iv) chloride (L~CN))_2Sn(Cl)SiPh_3 (7) which was then oxidized to (L~CN))_2Sn(Cl)OSiPh_3 (8). The unprecedented reaction of 1 with (n-Bu)3SnCl provided the distannane (L~CN))_2Sn(Cl)SnBu3 (9) which could be oxidized by dioxygen to a distannoxane (L~CN))_2Sn(Cl)OSnBu 3 (10). In addition, the solid-state structures of 3, 5, 6 and 8 were determined by the X-ray diffraction techniques.
机译：研究了（L〜CN）_2_2Sn（1）（其中L〜CN为2-（N，N-二甲基氨基甲基）苯基-）对各种含有E-Cl键的底物的反应性（E = C ，Si，Ge和Sn）。烷基氯（如氯仿或二氯甲烷）与1反应生成（L〜CN））_ 2SnCl_2，副产物收率不高。苯甲酰氯在低温下与1反应生成热不稳定产物（L〜CN））_ 2Sn（Cl）C（O）Ph（2），该产物经多核NMR光谱学和X射线衍射技术分离并表征。 2中中心锡原子的附近显示出三角双锥几何形状。尝试用双氧将2氧化，得到相应的有机锡（iv）苯甲酸酯。另一方面，原位制备的（L〜CN））_ 2SnO（由1与双氧反应合成）与PhCOCl的反应导致形成所需的有机锡（iv）苯甲酸酯（L〜CN））_ 2Sn （Cl）C（O）OPh（3）。 1与Ph_3GeCl的反应生成三苯基锗烷基取代的二有机锡（iv）氯化物（L〜CN））_ 2Sn（Cl）GePh_3（4），随后得到混合的二有机锡（iv）氯化物氧化物[（L〜（CN））_ 2SnCl]在空气中失去GePh 3部分后，将产生_2O（5）。当在苯而不是氯仿中进行相同的反应时，获得了独特的[Ph_3Ge] _4 [Sn_6O_8]簇（6）。同样，1与Ph_3SiCl的反应提供了三苯基甲硅烷基取代的二有机锡（iv）氯化物（L〜CN））_ 2Sn（Cl）SiPh_3（7），然后被氧化为（L〜CN））_ 2Sn（Cl）OSiPh_3（8） 。 1与（n-Bu）3SnCl的空前反应提供了二锡烷（L〜CN））_ 2Sn（Cl）SnBu3（9），它可以被双氧氧化为二锡烷（L〜CN））_ 2Sn（Cl）OSnBu 3 （10）。另外，通过X射线衍射技术确定了3、5、6和8的固态结构。

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