Fleischmann, Martin and Dielmann, Fabian and Balazs, Gabor and Scheer, Manfred (2016) Oxidation Chemistry of Inorganic Benzene Complexes. CHEMISTRY-A EUROPEAN JOURNAL, 22 (43). pp. 15248-15251. ISSN 0947-6539, 1521-3765
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The oxidation of the 28 VE cyclo-E-6 triple-decker complexes [((CpMo)-Mo-R)(2)(mu,eta(6):eta(6)-E-6)] (E = P, Cp-R = Cp(2a), Cp*(2b), Cp-Bn(2c)= C-5(CH2Ph)(5); E = As, Cp-R = Cp*(3)) by Cu+ or Ag+ leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry ( CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E-6 middle decks of the oxidized complexes are distorted to a quinoid ( 2a) or bisallylic ( 2b, 2c, 3) geometry. DFT calculations of 2a, 2b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the sigma-system of the cyclo-E-6 ligands in 2a-3. Among the starting complexes, 2c is reported for the first time including its preparation and full characterization.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DECKER SANDWICH COMPLEXES; COORDINATION BEHAVIOR; LIGAND COMPLEXES; CATIONS; PENTAPHOSPHAFERROCENE; REDOX; HEXAPHOSPHABENZENE; PHOSPHORUS; ACTIVATION; CU+; inorganic benzene; isolobal analogy; oxidation; phosphorus; triple-decker sandwich complexes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 15 Mar 2019 12:08 |
| Last Modified: | 15 Mar 2019 12:08 |
| URI: | https://pred.uni-regensburg.de/id/eprint/4232 |
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