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A Dinuclear Double‐Stranded Oxido Complex of Re V with a Bis(benzene‐ o ‐dithiolato) Ligand
Author(s) -
Gancheff Jorge S.,
Albuquerque Rodrigo Q.,
GuerreroMartínez Andrés,
Pape Tania,
De Cola Luisa,
Hahn F. Ekkehardt
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900496
Subject(s) - chemistry , natural bond orbital , crystallography , ligand (biochemistry) , singlet state , rhenium , atomic orbital , density functional theory , metal , molecular orbital , double bond , luminescence , computational chemistry , molecule , electron , atomic physics , inorganic chemistry , excited state , biochemistry , physics , receptor , optoelectronics , organic chemistry , quantum mechanics , polymer chemistry
The reaction of [ReOCl 3 (PPh 3 ) 2 ] with 1,2‐bis(2,3‐dimercaptobenzamido)ethane (H 4 ‐ 1 ) in the presence of Na 2 CO 3 in methanol under anaerobic conditions affords the dinuclear Re V oxido complex [PPh 4 ] 2 [ReO( 1 )] 2 containing two distorted square‐pyramidal {Re V OS 4 } units bridged by the ligand strands in a double‐stranded fashion. The coordinationgeometry around the metal centers is similar to the one observed for [ReO(bdt) 2 ] – . The ReS 4 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 experimental 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 Re V 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.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)