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Molecular and Electronic Structure of Re2Br4(PMe3)(4)
Univ Nevada, Dept Chem, Las Vegas, NV 89154 USA.;Univ Sheffield, Dept Mat Sci & Engn, Sheffield S1 3JD, S Yorkshire, England..
Univ Nevada, Dept Chem, Las Vegas, NV 89154 USA..
UPMC, CNRS, Coll France, Lab Chim Proc Biol,UMR 8229, 11 Pl Marcelin Berthelot, F-75231 Paris 05, France..ORCID iD: 0000-0002-7731-6498
Univ Nevada, Dept Chem, Las Vegas, NV 89154 USA..
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2016 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 55, no 14, 7111-7116 p.Article in journal (Refereed) Published
Abstract [en]

The dinuclear rhenium(II) complex Re2Br4(PMe3)(4) was prepared from the reduction of [Re2Br8](2-) with (n-Bu4N)BH4 in the presence of PMe3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV-visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re-Re distance (2.2521(3) angstrom) is slightly longer than the one in Re2Cl4(PMe3)(4) (2.247(1) angstrom). The molecular and electronic structure of Re2X4(PMe3)(4) (X = Cl, Br) were studied by multiconfigurational quantum chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re2Cl4(PMe3)(4). The electronic absorption spectrum of Re2Br4(PMe3)(4) was recorded in benzene and shows a series of low-intensity bands in the range 10 000-26 000 cm(-1). The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. Calculations predict that the lowest energy band corresponds to the delta* -> sigma* transition, while the next higher energy bands were attributed to the delta* -> pi*, delta -> sigma*, and delta -> pi* transitions.

Place, publisher, year, edition, pages
2016. Vol. 55, no 14, 7111-7116 p.
National Category
Theoretical Chemistry
URN: urn:nbn:se:uu:diva-308260DOI: 10.1021/acs.inorgchem.6b01052ISI: 000380181400039PubMedID: 27387436OAI: oai:DiVA.org:uu-308260DiVA: diva2:1049316
Swedish Research Council, 2012-3910eSSENCE - An eScience CollaborationKnut and Alice Wallenberg Foundation, KAW-2013.0020
Available from: 2016-11-24 Created: 2016-11-24 Last updated: 2016-12-02Bibliographically approved

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Todorova, Tanya K.Sørensen, Lasse K.Fernández Galván, IgnacioLindh, Roland
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