Molecular Structure of tert-Butylazide: A Gas-Phase Electron Diffraction and Quantum Chemical Study期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

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Molecular Structure of tert-Butylazide: A Gas-Phase Electron Diffraction and Quantum Chemical Study

Authors:	Annemarie MacKenzie Thomas M Klapötke György Schultz Magdolna Hargittai

Institution:	(1) Institute of Inorganic Chemistry, University of Munich (L.M.U.), Meiserstrasse 1, Munich, D-80333, Germany;(2) Structural Chemistry Research Group of the Hungarian Academy of Sciences, Eötvös University, Pf. 117, H-1431 Budapest, Hungary

Abstract:	The molecular structure of tert-butylazide has been determined by gas-phase electron diffraction and quantum chemical calculations. The HF/6-31G* and B3LYP/6-31G** calculations yielded near C _s symmetry for the tert-butyl group, anti conformation of the (C)N—N bond with respect to one of the $({\text{N}}){\text{C}}{\kern 1pt} - {\kern 1pt} {\text{C}}({\text{H}}_3 )$ bonds, and an essentially free rotation around the $({\text{C}}){\text{N}}{\kern 1pt} - {\kern 1pt} {\text{N}}({\text{N}})$ bond with a 0.34 kcal/mol energy difference between syn and anti conformations of the CNNN moiety, the anti being the more stable form. The electron diffraction analysis was carried out by modeling a mixture of conformational isomers, generated by rotating the terminal nitrogen of the azide group, using a computed rotational potential. The data are consistent with C _s symmetry for the tert-butyl group. The $({\text{C}}){\text{N}}{\kern 1pt} - {\kern 1pt} {\text{N}}$ bond, however, was found to be rotated out of the anti position, with respect to one of the $({\text{N}}){\text{C}}{\kern 1pt} - {\kern 1pt} {\text{CH}}_3$ bonds, by 12.5(12)°. The electron diffraction analysis yielded the following bond lengths (r _g), bond angles, and torsional angles: ${\text{C}}{\kern 1pt} - {\kern 1pt} {\text{H 1}}{\text{.111(5) }}{\AA}$ , $({\text{N}}{\kern 1pt} - {\kern 1pt} {\text{N}})_{{\text{terminal}}} {\text{ 1}}{\text{.143(4) }}{\AA}, (N{\kern 1pt} - {\kern 1pt} {\text{N}})_{central} {\text{ 1}}{\text{.240(5) }}{\AA}{\text{, (C}}{\kern 1pt} - {\kern 1pt} {\text{C)}}_{{\text{mean}}} {\text{ 1}}{\text{.534(3) }}{\AA}{\text{, N}}{\kern 1pt} - {\kern 1pt} {\text{N}}{\kern 1pt} - {\kern 1pt} {\text{N 171}}{\text{.8(20)}}^\circ {\text{, N}}{\kern 1pt} - {\kern 1pt} {\text{N}}{\kern 1pt} - {\kern 1pt} {\text{C 118}}{\text{.6()10}}^\circ {\text{, N}}{\kern 1pt} - {\kern 1pt} {\text{C}}{\kern 1pt} - {\kern 1pt} {\text{C 102}}{\text{.5(6)}}^\circ {\text{ and 110}}{\text{.5(4)}}^\circ {\text{, C}}{\kern 1pt} - {\kern 1pt} {\text{C}}{\kern 1pt} - {\kern 1pt} {\text{H 111}}{\text{.2(4)}}^\circ {\text{, C}}{\kern 1pt} - {\kern 1pt} {\text{C}}{\kern 1pt} - {\kern 1pt} {\text{C 110}}{\text{.2(7)}}^\circ {\text{ and 112}}{\text{.6(7)}}^\circ {\text{, N}}{\kern 1pt} - {\kern 1pt} {\text{N}}{\kern 1pt} - {\kern 1pt} {\text{C}}{\kern 1pt} - {\kern 1pt} {\text{C 167}}{\text{.5(12)}}^\circ {\text{, 50}}{\text{.1(6)}}^\circ {\text{, and - 75}}{\text{.2(10)}}^\circ$ .

Keywords:	Electron diffraction ab initio calculations tert-butylazide molecular structure
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