Synthesis, X-ray structure, and theoretical studies of novel cationic mono-cylopentadienyl complexes of Co(III): the orthometalation of trans-azobenzene

Citation:
Aviles, T., A. Dinis, M. J. Calhorda, P. Pinto, V. Felix, and M. G. B. Drew. "Synthesis, X-ray structure, and theoretical studies of novel cationic mono-cylopentadienyl complexes of Co(III): the orthometalation of trans-azobenzene." J Organomet Chem. 625 (2001): 186-194. copy at https://docentes.fct.unl.pt/p387/publications/synthesis-x-ray-structure-and-theoretical-studies-novel-cationic-mono-cylopentadie

Abstract:

New cationic mono-cyclopentadienyl complexes of Co(III) containing mono or bidentate nitrogen donor ligands of general formula [Co(eta (5)-C5H5)(PPh3)L-2][BF4](2) (L = NC-CH3, 2, and NC = Ph, 3) or [Co(eta (5)-C5H5)(PPh3)(L-L)[BF4](2), [L-L = 2,2 ' -bisimidazole (H(2)biim) (4) and dipyridylamine [HN(NC5H5)(2)] (5) have been synthesised by the stoichiometric reaction of the Co(III) complex Co(eta (5)-C5H5)(PPh3)I-2 (1), with Ag[BF4] and the appropriate ligand in CH2Cl2. Under the same conditions and using;trans-azobenzene as a ligand, an orthometalation reaction took placet giving the new compound [Co(eta (5)-C5H5)(PPh3)(kappa -C,kappa -N-C6H4N=NPh)][BF4] (6) in high yield. The structural characterisation of compounds 4 and 6, and of the starting compound Co(eta (5)-C5H5)(PPh3)I-2 (1) was done by single-crystal X-ray diffraction studies. DFT calculations (ADF program) were performed in order to understand the orthometallation reaction. (C) 2001 Elsevier Science B.V. All rights reserved.

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