Issue 8, 2002

Novel bis-arene (sandwich) complexes with NO+ acceptor. Isolation, X-ray crystallography and electronic structure

Abstract

The unusual charge-transfer complexes of various arene donors (ArH) with the nitrosonium cation (NO+) resulting from bimolecular [1 ∶ 1] associations can be extended at suitably high ArH concentrations to termolecular processes leading to the analogous [2 ∶ 1] complexes. Spectral analyses of the intense color changes accompanying the arene interaction with NO+ provide optimum conditions for the isolation of pure crystalline ternary complexes. Single crystal X-ray crystallographic determinations establish the unique sandwich structure consisting of the NO moiety interposed (parallel) between a pair of cofacial arene donors—reminiscent of the well-known transition metal sandwich complexes with aromatic ligands. The electronic structure associated with the arene binding to NO in the ternary complex is analyzed by the application of the semi-empirical LCAO molecular-orbital methodology and the Mulliken (charge-transfer) formulation of the electronic (UV–VIS–NIR) transitions. The resultant evaluation of the electronic coupling (matrix) elements HAB indicates strong donor/acceptor interactions of the frontier orbitals of the arene donor (HOMO) and nitrosonium acceptor (LUMO) that are only slightly less than those extant in the corresponding binary [1 ∶ 1] complexes.

Graphical abstract: Novel bis-arene (sandwich) complexes with NO+ acceptor. Isolation, X-ray crystallography and electronic structure

Supplementary files

Article information

Article type
Paper
Submitted
05 Mar 2002
Accepted
12 Jun 2002
First published
09 Jul 2002

J. Chem. Soc., Perkin Trans. 2, 2002, 1468-1474

Novel bis-arene (sandwich) complexes with NO+ acceptor. Isolation, X-ray crystallography and electronic structure

S. V. Rosokha, S. V. Lindeman and J. K. Kochi, J. Chem. Soc., Perkin Trans. 2, 2002, 1468 DOI: 10.1039/B202323G

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