New type of reactions of stannylenes with organic azides: Theoretical study

被引：6

作者：

Nechaev, Mikhail S. ^{[1
,2
]}

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[2] Russian Acad Sci, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2008年 / 862卷 / 1-3期

基金：

俄罗斯基础研究基金会;

关键词：

reaction mechanism; potential energy surface; stannylene; tin azide; stannaimine;

D O I：

10.1016/j.theochem.2008.04.024

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Density functional study of the reaction of Sn(OCH2CH2NMe2)(2) (1) with Me3Si-N-3 (2) yielding the redistribution product [(N-3)SnOCH2CH2NMe2](2) (3) has been performed at the PBE/TZ2P(SBKJC) level. Two possible reaction paths, the formation of [(N-3)SnOCH2CH2NMe2](2) (path A) and initially expected imine Me3Si-N=Sn(OCH2CH2NMe2)(2) (5) (path B), have been studied. The formation of the imine 5 is thermally more favorable than the formation of dimeric stannylene 3, Delta G(0)(5) = -6.7 kcal/mol and Delta G(0)(3) = -5.9 kcal/mol. The reaction proceeds to 3 due to a lower energy barrier, Delta G(double dagger) = 27.8 and 39.5 kcal/mol for 3 and 5, respectively. (C) 2008 Elsevier B.V. All rights reserved.

引用

页码：49 / 52

页数：4

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