Russian Chemical Bulletin

, Volume 44, Issue 6, pp 997–1004 | Cite as

Crown compounds for anions. The nature of chemical bonds in the complexes of halide anions with cyclic trimeric perfluoro-o-phenylenemercury and some of its analogs

  • A. L. Chistyakov
  • I. V. Stankevich
  • N. P. Gambaryan
  • I. A. Tikhonova
  • V. B. Shur
Physical Chemistry

Abstract

Geometries and electronic structures of the complexes of halide anions with cyclic trimerico-phenylenemercury, (o-C6H4Hg)3, perfluoro-o-phenylenemercury, (o-C6F4Hg)3, vinylenemercury, (C2H2Hg)3, and perfluorovinylenemercury, (C2F2Hg)3, were modelled by the MNDO method. Calculations were performed for [L-X] semisandwich complexes, [X-L-X]2− bipyramidal complexes, and [L-X-L] sandwich complexes (where X=Hal,L is a mercury-containing macrocycle). Based on the results of calculations, we concluded that it was advantageous to describe the chemical bonding between halide anions and mercury-containing macrocycles in terms of generalized chemical bonds, which were successfully used for π-complexes of transition metals. In the [L-X] semisandwich complexes, the halide anion and the metallacycle are involved in the formation of three generalized chemical bonds: one headlight-shaped σ-bond and two two-lobe π-bonds. In the [X-L-X]2− bipyramidal complexes, each halide anion forms three generalized chemical bonds with the macrocycle. It is possible because the macrocycleL has unoccupied molecular orbitals suitable for the formation of such bonds; these MOs consist mainly of the orbitals of mercury atoms directed toward both the upper and lower halogen atoms. In the [L-X-L] sandwich complexes, the halide anion cannot be bonded to each ringvia three bonds, and, hence, an unsymmetrical structure is formed, in which the rings are located at different distances from the central atom: the [L-X] semisandwich complex solvated by macrocycleL.

Key words

polymercury-containing macrocycles halide anions complexes MNDO method generalized chemical bond 

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Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • A. L. Chistyakov
    • 1
  • I. V. Stankevich
    • 1
  • N. P. Gambaryan
    • 1
  • I. A. Tikhonova
    • 1
  • V. B. Shur
    • 1
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation

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