title: Spectroscopic and computational investigations of stable radical anions of triosmium benzoheterocycle clusters.
abstract: The variable temperature (1)H and (13)C NMR and EPR spectra of the stable radical anions [Os(3)(CO)(9)(micro(3)-eta(2)-L)(micro-H)] (LH=phenanthridine, 1; 5,6-benzoquinoline, 2), and [Os(3)(CO)(10)(micro(3)-eta(2)-L)(micro-H)] (LH=quinoxaline, 3) are reported. The radical anions 1(-), 2(-), and 3(-) can be prepared by both exhaustive electrolysis and partially by chemical reduction with cobaltocene and with sodium dispersion (only with sodium dispersion in the case of 3(-)). DFT calculations on 1-3 reveal that the LUMO for the electron-deficient compounds 1 and 2 involves significant contributions from both the heterocyclic ligand and the two metal atoms bridged by the ligand and the micro-hydride. The character of this orbital rationalizes the previously observed regioselective reactions of these complexes with nucleophiles. In contrast, the LUMO for the electron precise 3 involves only ligand-based orbitals. Partial chemical reduction of 1 and 2 requires an excess of either cobaltocene or sodium, and their (1)H and (13)C NMR spectra reveal selective line broadening of those proton resonances that are predicted by DFT calculations to bear the greatest amount of free spin density. The variable temperature behavior of the partially chemically reduced species of 1 and 2 indicates that electron transfer between the reduced/unreduced cluster pair and between the cobaltocene/cobaltocenium pair occurs on the NMR timescale. The radical anions of 1 and 2 prepared by exhaustive electrolysis show an EPR signal at room temperature, while the NMR signals are uniformly broadened. Compound 3 appears to be partially reduced by sodium at room temperature and shows uniformly broadened (1)H NMR resonances at room temperature that sharpen significantly at -80 degrees C. The temperature dependence of the spectra are discussed in terms of the effects of relative electron nuclear relaxation processes, chemical exchange, and the results of the DFT calculations.
authors.affiliation: Dipartimento di Chimica IFM, Università di Torino, via P. Giuria 7, 10125 Torino, Italy.
authors.forename: Carlo
authors.initials: C
authors.lastname: Nervi
authors.forename: Roberto
authors.initials: R
authors.lastname: Gobetto
authors.forename: Luciano
authors.initials: L
authors.lastname: Milone
authors.forename: Alessandra
authors.initials: A
authors.lastname: Viale
authors.forename: Edward
authors.initials: E
authors.lastname: Rosenberg
authors.forename: Dalia
authors.initials: D
authors.lastname: Rokhsana
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler
mesh_terms: D000838:Anions / Q000737:chemistry; D001554:Benzene / Q000737:chemistry* / Q000378:metabolism; D019295:Computational Biology; D006571:Heterocyclic Compounds / Q000737:chemistry* / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D017892:Osmium Compounds / Q000737:chemistry* / Q000378:metabolism; D010617:Phenanthridines / Q000737:chemistry; D011804:Quinolines / Q000737:chemistry
chemical_list: D000838:Anions; D006571:Heterocyclic Compounds; D017892:Osmium Compounds; D010617:Phenanthridines; D011804:Quinolines; C039108:benzo(f)quinoline; D001554:Benzene