A Dinuclear Double-Stranded Oxido Complex of ReV with a Bis(benzene-o-dithiolato) Ligand

COMPLEJO DE OXIDO

RENIO

BIBLIOGRAFIA NACIONAL QUÍMICA

2009

The reaction of [ReOCl3(PPh3)2] with 1,2-bis(2,3-dimercaptobenzamido) ethane (H4-1) in the presence of Na2CO3 in methanol under anaerobic conditions affords the dinuclear ReV oxido complex [PPh4]2[ReO(1)]2 containing two distorted square-pyramidal {ReVOS4} units bridged by the ligand strands in a double-stranded fashion. The coordination geometry around the metal centers is similar to the one observed for [ReO(bdt)2]–. The ReS4 planes are arranged in a coplanar fashion and are not twisted around the metal–metal vector, which prevents the complex to adopt a helical structure. Luminescence studies show the presence of emission bands, which are assigned to singlet-singlet transitions exhibiting very fast decays (ca. 10 ns). Theoretical Density Functional (DFT) studies on geometry and electronic properties were performed employing the hybrid B3LYP and PBE1PBE functionals. While the general trends observed in the experi- Introduction Oxido complexes of ReV have received considerable attention in the past few years. Particular interests have been aroused due to their reactivity, their photochemical and spectroscopic properties and their role in catalytic processes and oxygen atom transfer (OAT) reactions.[1–9] Furthermore, due to the nuclear decay of 186Re, rhenium complexes found very promising radiopharmaceutical applications.[ 10–13] Rhenium oxido complexes containing dithiolato ligands in particular, have been studied with different purposes. For example, mechanistic aspect of OAT reactions have been studied with complexes of type [Re- O(CH3)(SCH2C6H4S)X] (X = substituted pyridine or alkyl and aryl phosphanes) by Lathi and Espenson,[14] and a comprehensive DFT study on these systems has been carried out Yang and Hall.[15] Noll[16] et al. have synthesized [a] Institut für Anorganische und Analytische Chemie der Westfälischen Wilhelms-Universität Münster, Corrensstrasse 30, 48149 Münster, Germany Fax: +49-251-833-3108 E-mail: fehahn@uni-muenster.de [b] Physikalisches Institut, Westfälische Wilhelms-Universität Münster, Mendelstrasse 7, 48149 Münster, Germany Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ejic.200900496. Eur. J. Inorg. Chem. 2009, 4043–4051 © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4043 mental data are well reproduced in all cases, a good agreement was obtained using PBE1PBE, in particular for the Re– S bonds. Natural Bond Orbitals (NBO) analysis indicates the presence of polarized Re
O and Re–S bonds, both of them polarized toward the non-metal. The calculation show that the molecular orbitals of the ReV are doubly degenerated, the occupied 5d orbital of rhenium lying beneath occupied sulfur- based MOs due to the rigid geometry imposed by the C– C backbone of the bis(benzene-o-dithiolato) ligands. The origin of all absorption bands is ascribed to a ligand-to-metal charge transfer (LMCT), in which occupied sulfur-based orbitals and unoccupied rhenium-centered orbitals are involved.

European Journal of Inorganic Chemistry no. 27, 2009. -- p.4043-4051

Willey

2009

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DOI: 10.1002/ejic.200900496