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Conformational and Bonding Properties of 3,3-Dimethyl- and 6,6-Dimethyl-1,5-diazabicyclo[3.1.0]hexane: A Case Study Employing the Monte Carlo Method in Gas Electron Diffraction.

Conformational and Bonding Properties of 3,3-Dimethyl- and 6,6-Dimethyl-1,5-diazabicyclo[3.1.0]hexane: A Case Study Employing the Monte Carlo Method in Gas Electron Diffraction.

Authors :
Vishnevskiy YV
Schwabedissen J
Rykov AN
Kuznetsov VV
Makhova NN
Source :
The journal of physical chemistry. A [J Phys Chem A] 2015 Nov 05; Vol. 119 (44), pp. 10871-81. Date of Electronic Publication: 2015 Oct 23.
Publication Year :
2015

Abstract

Gas-phase structures of two isomers of dimethyl-substituted 1,5-diazabicyclo[3.1.0]hexanes, namely, 3,3-dimethyl- and 6,6-dimethyl-1,5-diazabicyclo[3.1.0]hexane molecules, have been determined by gas electron diffraction method. A new approach based on the Monte Carlo method has been developed and used for the analysis of precision and accuracy of the refined structures. It was found that at 57 °C 3,3-dimethyl derivative exists as a mixture of chair and boat conformers with abundances 68(8)% and 32(8)%, respectively. 6,6-Dimethyl-1,5-diazabicyclo[3.1.0]hexane at 50 °C has only one stable conformation with planar 5-ring within error limits. Theoretical calculations predict that the 6,6-dimethyl isomer is more stable in comparison to the 3,3-dimethyl isomer with energy difference 3-5 kcal mol(-1). In order to explain the relative stability and bonding properties of different structures the natural bond orbitals (NBO), atoms in molecules (AIM), and interacting quantum atoms (IQA) analyses were performed.

Details

Language :
English
ISSN :
1520-5215
Volume :
119
Issue :
44
Database :
MEDLINE
Journal :
The journal of physical chemistry. A
Publication Type :
Academic Journal
Accession number :
26461037
Full Text :
https://doi.org/10.1021/acs.jpca.5b08228