Reduction of [Cp* 2 Mo 2 O 5 ] in Aqueous Medium: Structure and Properties of a Triangular Mixed Oxo‐Hydroxo‐Bridged Product, [Cp* 3 Mo 3 (μ‐O) 2 (μ‐OH) 4 ](X) 2 (X = CF 3 CO 2 or CF 3 SO 3 )

Autor: Rinaldo Poli, Jean-Claude Daran, Miguel Baya, Funda Demirhan, Bahar Çağatay, Deniz Demir
Rok vydání: 2006
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2006:757-764
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.200500665
Popis: The reduction of [Cp*2Mo2O5] with Zn in a MeOH/H2O solution acidified with either CF3COOH or CF3SO3H leads to the formation of the [Cp*3Mo3(μ-O)2(μ-OH)4]2+ ion as its trifluoroacetate or trifluoromethanesulfonate salt. The structure of the compound was confirmed by X-ray analyses. The anions establish hydrogen-bonding interactions with all four bridging OH groups. Density functional calculations afford bonding parameters in close agreement with the observed structure and indicate that the cluster is best described as a valence-delocalized Mo313+ species. The five metal electrons are distributed among an a-type (z2) orbital, which accounts for most of the metal–metal attraction, and two essentially metal–metal nonbonding e-type (xy) orbitals with a slight Mo-(μ-O) π*-type contribution. Because of the C2 symmetry, the latter orbitals are not degenerate. The calculations show that the unpaired electron is located in a molecular orbital with equal contribution from two Mo atoms, in agreement with the experimental observation of coupling of the unpaired electron to two Mo atoms in the isotropic EPR spectrum. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Databáze: OpenAIRE
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