3-丁炔-1-硒醇（HSeCH2CH2C≡CH）的微波光谱和量子化学研究

A microwave spectroscopic and quantum chemical study of 3-butyne-1-selenol (HSeCH2CH2C[triple bond]CH).

作者信息

Møllendal Harald, Mokso Rajmund, Guillemin Jean-Claude

机构信息

Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P. O. Box 1033 Blindern, NO-0315 Oslo, Norway.

出版信息

J Phys Chem A. 2008 Apr 10;112(14):3053-60. doi: 10.1021/jp7112973. Epub 2008 Mar 11.

DOI:10.1021/jp7112973

PMID:18331012

Abstract

The microwave spectrum of 3-butyne-1-selenol has been studied by means of Stark-modulation microwave spectroscopy and quantum chemical calculations employing the B3LYP/aug-cc-pVTZ and MP2/6-311++G(3df,3pd) methods. Rotational transitions attributable to the H80SeCH2CH2C[triple bond]CH and H78SeCH2CH2C[triple bond]CH isotopologues of two conformers of this molecule were assigned. One of these conformers possesses an antiperiplanar arrangement for the atoms Se-C-C-C, while the other is synclinal and seems to be stabilized by the formation of a weak intramolecular hydrogen bond between the hydrogen atom of the selenol group and the pi electrons of the CC triple bond. The energy difference between these conformers was determined to be 0.2(5) kJ/mol by relative intensity measurements, and the hydrogen-bonded form was slightly lower in energy.

摘要

通过斯塔克调制微波光谱法以及采用B3LYP/aug-cc-pVTZ和MP2/6-311++G(3df,3pd)方法的量子化学计算，对3-丁炔-1-硒醇的微波光谱进行了研究。归属了该分子两个构象异构体的H80SeCH2CH2C≡CH和H78SeCH2CH2C≡CH同位素异构体的转动跃迁。其中一个构象异构体中Se-C-C-C原子呈反式共平面排列，而另一个是顺错式，似乎通过硒醇基团的氢原子与碳碳三键的π电子之间形成弱分子内氢键而得以稳定。通过相对强度测量确定这两个构象异构体之间的能量差为0.2(5) kJ/mol，且氢键形式的能量略低。