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Molecular and electronic structure of Re2Br4(PMe3)4

Journal Article · · Inorganic Chemistry
 [1];  [1];  [2];  [1];  [3];  [3];  [3];  [1];  [4]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. College de France, Paris Cedex (France)
  3. Uppsala Univ., Uppsala (Sweden)
  4. Univ. of Nevada, Las Vegas, NV (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations
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) Å) is slightly longer than the one in Re2Cl4(PMe3)4 (2.247(1) Å). 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. As a result, calculations predict that the lowest energy band corresponds to the δ* → σ* transition, while the next higher energy bands were attributed to the δ* → π*, δ → σ*, and δ → π* transitions.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
Knut and Alice Wallenberg Foundation; Swedish Research Council; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) - Single Investigator and Small Group Research (SISGR); Uppsala University
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1339564
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 55; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
Rhenium
electronic structure
metal-metal bonds
single crystal X-ray diffraction