title: Oxidation Chemistry of Inorganic Benzene Complexes.
abstract: The oxidation of the 28 VE cyclo-E6triple-decker complexes [(CpRMo)2(μ,η6:η6-E6)] (E=P, CpR=Cp(2 a), Cp*(2 b), CpBn(2 c)=C5(CH2Ph)5; E=As, CpR=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-E6middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E6ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization.
authors: Department of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
authors: Martin
authors: M
authors: Fleischmann
authors: Department of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
authors: Fabian
authors: F
authors: Dielmann
authors: Department of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
authors: Gábor
authors: G
authors: Balázs
authors: Department of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany. manfred.scheer@ur.de.
authors: Manfred
authors: http://orcid.org/0000-0003-2182-5020
authors: M
authors: Scheer
keywords: inorganic benzene; isolobal analogy; oxidation; phosphorus; triple-decker sandwich complexes