Tautomeric properties and gas-phase structure of 3-methyl-2,4-pentanedione

被引：3
作者：
Belova, Natalya V. [1 ]
Girichev, Georgiy V. [1 ]
Oberhammer, Heinz [2 ]
Nguen Hoang Trang [1 ]
Shlykov, Sergey A. [1 ]
机构：
[1] Ivanovo State Univ Chem & Technol, Res Inst Thermodynam & Kinet Chem Proc, Ivanovo 153460, Russia
[2] Univ Tubingen, Inst Phys & Theoret Chem, D-72076 Tubingen, Germany
来源：
JOURNAL OF MOLECULAR STRUCTURE | 2012年 / 1023卷
基金：
俄罗斯基础研究基金会;
关键词：
beta-Diketones; Tautomerism; Electron diffraction; Quantum chemical calculations; Molecular structure; KETO-ENOL-TAUTOMERISM; MAGNETIC-RESONANCE-SPECTROSCOPY; BETA-DIKETONES; VIBRATIONAL ASSIGNMENT; HYDROGEN-BOND; ACETYLACETONE; FORM; COVALENT; DFT;
D O I：
10.1016/j.molstruc.2012.03.065
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 tautomeric and structural properties of 3-methyl-2,4-pentanedione, CH3-C(O)-CH(CH3)-C(O)-CH3, have been studied by gas-phase electron diffraction (GED) and quantum chemical calculations (B3LYP and MP2 approximation with different basis sets up to aug-cc-pVTZ). Analysis of GED intensities resulted in the presence of 100(3)% enol tautomer at 274(7)K. Quantum chemical calculations predict enol concentrations from 8% at MP216-31G(d,p) level to 100% at B3LYP/aug-cc-pVTZ. This would show the failure of the MP2/6-31G(d,p) method. The enol ring possesses C-s symmetry with a strongly asymmetric hydrogen bond. The experimental geometric parameters are reproduced very closely by the B3LYP/aug-cc-pVTZ method. (C) 2012 Elsevier B.V. All rights reserved.
引用
收藏
页码：49 / 54
页数：6
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