Structural trends of 29Si-1H spin-spin coupling constants across double bond

被引：14
|
作者：
Rusakov, Yury Yu [1 ]
Krivdin, Leonid B. [1 ]
Nosova, Valentina M. [2 ]
Kisin, Alexander V. [2 ]
Lakhtin, Valentin G. [2 ]
机构：
[1] Russian Acad Sci, AE Favorsky Irkutsk Inst Chem, Siberian Branch, Irkutsk 664033, Russia
[2] State Res Inst Chem & Technol Organoelement Cpds, Moscow 105118, Russia
来源：
MAGNETIC RESONANCE IN CHEMISTRY | 2012年 / 50卷 / 10期
基金：
俄罗斯基础研究基金会;
关键词：
NMR; 29Si-1H spin-spin coupling constants; SOPPA; NJC analysis; alkenylmethylsilanes; alkenylchlorosilanes; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; CONFORMATIONAL-ANALYSIS; BEHAVIOR; ASSIGNMENTS;
D O I：
10.1002/mrc.3860
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The calculations of geminal and vicinal 29Si1H spinspin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second-order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J-coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal 29Si1H spinspin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding SiC and CH orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding SiCl orbitals. Copyright (c) 2012 John Wiley & Sons, Ltd.
引用
收藏
页码：665 / 671
页数：7
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