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硅(三甲基硅基)二苯基硅烷 - 一种新型低价锡簇化合物的配体。

Si(SiMe3)2SiPh3 - a ligand for novel sub-valent tin cluster compounds.

作者信息

Klink R, Schrenk C, Schnepf A

机构信息

Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany.

出版信息

Dalton Trans. 2014 Nov 14;43(42):16097-104. doi: 10.1039/c4dt02372b.

Abstract

For the synthesis of metalloid tin cluster compounds applying the disproportionation reaction of a Sn(i) halide, silyl ligands, especially the symmetric Si(SiMe3)3 has proven to be extremely useful. Silyl ligands of lower symmetry where e.g. one SiMe3 group is substituted with SiPh3 are thereby unexplored, although the synthesis of the anionic silyl precursors is quite easy, referring to previously described methods. Here the synthesis of the silanide Si(SiMe3)2(SiPh3) as its potassium () as well as its lithium salt () in excellent yield is presented. proved to be a suitable starting material for the synthesis of subvalent tin compounds as shown by the reaction with tin halides in oxidation state +2 (SnCl2) and +1 (SnCl); i.e. on the one hand the anticipated stannide Sn(Si(SiMe3)2SiPh3)2Cl could be isolated and on the other hand the unexpectedly partly substituted ring compound Cl4Sn4[Si(SiMe3)2SiPh3]4 is obtained. As no elemental tin is formed during the reaction with SnCl, metalloid tin clusters may be present in solution too, which is supported by the nearly black color of the reaction mixture, showing that might be a suitable ligand for the synthesis of such cluster compounds.

摘要

对于应用卤化亚锡歧化反应合成类金属锡簇化合物而言,硅烷基配体,尤其是对称的Si(SiMe3)3已被证明极为有用。尽管参照先前所述方法,阴离子型硅烷基前体的合成相当容易,但对称性较低的硅烷基配体,例如其中一个SiMe3基团被SiPh3取代的配体尚未得到探索。本文展示了以优异产率合成硅化物[Si(SiMe3)2(SiPh3)]-的钾盐以及锂盐。事实证明,它是合成低价态锡化合物的合适起始原料,这一点通过其与氧化态为+2(SnCl2)和+1(SnCl)的卤化锡反应得以体现;即一方面可以分离出预期的锡化物[Sn(Si(SiMe3)2SiPh3)2Cl]-,另一方面可以得到意外的部分取代的环状化合物Cl4Sn4[Si(SiMe3)2SiPh3]4。由于在与SnCl反应过程中未形成元素锡,溶液中可能也存在类金属锡簇,反应混合物近乎黑色的颜色证明了这一点,表明其可能是合成此类簇化合物的合适配体。

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