Computational characterisation of the charge-transfer and T-shaped molecular complexes of N-methyl imidazoline-2-thione and N-methyl imidazolidine-2-thione with the dihalogens Br₂ and I₂

Abstract

The computational characterisation of the molecular complexes of N-methyl imidazoline-2-thione (methimazole) and the related saturated analogue N-methyl imidazolidine-2-thione with Br₂ and I₂ is carried out using quantum mechanical electronic structure methods. Two kinds of molecular connectivity have been examined. The first displays a collinear S–X–X geometry (X = Br, I) and leads to charge-transfer (CT) type adducts, possible in two stereoisomeric conformations depending on the direction of the X₂-axis, either planar or perpendicular to the NCS plane. The second kind corresponds to T-shaped hypervalent complexes in which sulphur is connected to both the X atoms forming the linear X–S–X arrangement. The structural changes, the spectroscopic findings, the natural bond orbital analysis and the examination of the molecular orbital second-order perturbation energies give interesting information about the nature of the halogen bonding interaction between the electron-donor organic species and the electron-acceptor dihalogen molecule. Similar trends are followed by the energy and relative stability results including basis set superposition error corrections, which show the larger stabilisation of the planar CT conformers of both dihalogens vs. the perpendicular configurations. They also indicate the higher stability of the T-shaped bromine complexes relative to the CT species, opposite to the energy order of the corresponding diiodine adducts. A critical comparison is carried out with literature results on similar systems.

Keywords:

• halogen bonding
• charge transfer
• hypervalent complexes

Acknowledgements

Computer services provided by the University of Ioannina Computer Center are gratefully acknowledged.