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Spectroscopic and Computational Investigations of Stable Radical Anions of Triosmium Benzoheterocycle Clusters
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SYSNO ASEP 0181838 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Ostatní články Title Spectroscopic and Computational Investigations of Stable Radical Anions of Triosmium Benzoheterocycle Clusters Author(s) Nervi, C. (IT)
Gobetto, R. (IT)
Milone, L. (IT)
Viale, A. (IT)
Rosenberg, E. (US)
Rokhsana, D. (US)
Fiedler, Jan (UFCH-W) RID, ORCIDSource Title Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 9, - (2003), s. 5749-5756Number of pages 8 s. Language eng - English Country DE - Germany Keywords cluster compounds ; electron transfer ; osmium Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects OC D15.10 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) GA203/03/0821 GA ČR - Czech Science Foundation (CSF) CEZ AV0Z4040901 - UFCH-W Annotation The radical anions 1ů, 2ů and 3ů 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 3ů). DFT calculations on 1 ů 3 reveal that the LUMO for the electron deficient 1 and 2 involves significant contributions from both the heterocyclic ligand and the two metal atoms bridged by the ligand and the -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 1H and 13C 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2004
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