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β-二酮亚胺锡(II)二甲酰胺 LSnNMe₂[L = HC(CMeNAr)₂; Ar = 2,6-iPr₂C₆H₃]与酮和炔烃的反应。

Reaction of β-diketiminate tin(II) dimethylamide LSnNMe₂ [L = HC(CMeNAr)₂; Ar = 2,6-iPr₂C₆H₃] with ketones and alkynes.

机构信息

Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077, Göttingen, Germany.

出版信息

Dalton Trans. 2010 May 21;39(19):4647-50. doi: 10.1039/c002849e.

Abstract

The reactions of stable β-diketiminate tin(II) dimethylamide LSnNMe₂ [L = HC(CMeNAr)₂; Ar = 2,6-iPr₂C₆H₃] (1) with ketones and activated terminal alkynes are described. 1 reacts with 2-benzoylpyridine and 2,2,2-trifluoroacetophenone to give the tin(II)-alkoxides LSnOCPh(2-Py)NMe₂ (2) and LSnOCPh(CF₃)NMe₂ (3), respectively, by nucleophilic addition of the dimethylamido group to the carbonyl moiety. Furthermore, the reaction of 1 with terminal alkynes (HCCCO₂R, R = Me, Et) forms tin(II)-alkynyl LSnCCCO₂R (R= Me, (4); R = Et, (5)) compounds under elimination of Me₂NH rather than undergoing a nucleophilic addition reaction at the carbon–carbon triple bond. Compounds 2-5 were characterized by microanalysis and multinuclear NMR spectroscopy. Moreover, 2 and 5 could be crystallized and their constitutions were confirmed by X-ray structural analysis. 2 and 5 are monomers in the solid state and the metal atom shows a distorted trigonal-pyramidal coordination sphere.

摘要

稳定的β-二酮亚胺锡(II)二甲酰胺 LSnNMe₂ [L = HC(CMeNAr)₂; Ar = 2,6-iPr₂C₆H₃](1)与酮和活化的末端炔烃的反应被描述。1 与 2-苯甲酰基吡啶和 2,2,2-三氟苯乙酮反应,通过二甲酰胺基对羰基部分的亲核加成,分别得到锡(II)-烷氧基化物 LSnOCPh(2-Py)NMe₂(2)和 LSnOCPh(CF₃)NMe₂(3)。此外,1 与末端炔烃(HCCCO₂R,R = Me,Et)反应,在消除 Me₂NH 的情况下形成锡(II)-炔基 LSnCCCO₂R(R= Me,(4);R = Et,(5))化合物,而不是在碳-碳三键上进行亲核加成反应。化合物 2-5 通过微量分析和多核 NMR 光谱进行了表征。此外,2 和 5 可以结晶,通过 X 射线结构分析确定了它们的结构。2 和 5 在固态下为单体,金属原子呈现出扭曲的三角双锥配位场。

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