Andrea Albertino, C. Garino, S. Ghiani
Feb 15, 2007
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Influential Citations
60
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Journal
Journal of Organometallic Chemistry
Abstract
Abstract We report a combined experimental and computational study of new rhenium tricarbonyl complexes based on the bidentate heterocyclic N–N ligands 2-(4-methylpyridin-2-yl)benzo[ d ]-X-azole (X = N–CH 3 , O, or S) and 2-(benzo[ d ]-X-azol-2-yl)-4-methylquinoline (X = N–CH 3 , O, or S). Two sets of complexes are reported. Chloro complexes, described by the general formula Re(CO) 3 [2-(4-methylpyridin-2-yl)benzo[ d ]-X-azole]Cl (X = N–CH 3 , 1 ; X = O, 2 ; X = S, 3 ) and Re(CO) 3 [2-(benzo[ d ]-X-azol-2-yl)-4-methylquinoline]Cl (X = N–CH 3 , 4 ; X = O, 5 ; X = S, 6 ) were synthesized heating at reflux Re(CO) 5 Cl with the appropriate N–N ligand in toluene. The corresponding pyridine set {Re(CO) 3 [2-(4-methylpyridin-2-yl)benzo-X-azole]py}PF 6 (X = N–CH 3 , 7 ; X = O, 8 ; X = S, 9 ) and {Re(CO) 3 [2-(benzo[ d ]-X-azol-2-yl)-4-methylquinoline]py}PF 6 (X = N–CH 3 , 10 ; X = O, 11 ; X = S, 12 ) was synthesized by halide abstraction with silver nitrate of 1 – 6 followed by heating in pyridine and isolated as their hexafluorophosphate salts. All complexes have been fully characterized by IR, NMR, electrochemical techniques and luminescence. The crystal structures of 1 and 7 were obtained by X-ray diffraction. DFT and time-dependent (TD) DFT calculations were carried out for investigating the effect of the organic ligand on the optical properties and electronic structure of the reported complexes.