Ab initio SCF study of the barrier to internal rotation in simple amides. Part 3. Thioamides

被引：7

作者：

Vassilev, NG ^{[1
]}

Dimitrov, VS ^{[1
]}

机构：

[1] Bulgarian Acad Sci, Inst Organ Chem, Sofia 1113, Bulgaria

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2003年 / 654卷 / 1-3期

关键词：

thioamides; barrier to internal rotation; ab initio SCF study;

D O I：

10.1016/S0022-2860(03)00177-7

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：

The free energies of activation for rotation about the thiocarbonyl C-N bond in X-C(S)N(CH3)(2) (X = H, F, Cl, CH3, CF3) were calculated at the MP2(fc)/6-31 + G*//6-31G* and MP2(fc)/6-311++G**//6-311++G** levels and compared with literature NMR gas-phase data. The results of calculations indicate that the nonbonded interactions in ground state (GS) are mainly responsible for the differences in the rotational barriers. For X = H, CH3 and CF3, the anti transition state (TS) is more stable; for the case X = Cl, the syn TS is more stable, while for the X = F, the two TS are energetically almost equivalent. (C) 2003 Elsevier Science B.V. All rights reserved.

引用

页码：27 / 34

页数：8