Molecular and electronic structure of Re2Br4(PMe3)4
Abstract
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 themore »
- Authors:
-
- Univ. of Nevada, Las Vegas, NV (United States)
- College de France, Paris Cedex (France)
- Uppsala Univ., Uppsala (Sweden)
- Univ. of Nevada, Las Vegas, NV (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Swedish Research Council (SRC); Uppsala University; Knut and Alice Wallenberg Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1339564
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 14; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Rhenium; DFT; electronic structure; metal-metal bonds; single crystal X-ray diffraction
Citation Formats
Johnstone, Erik V., Poineau, Frederic, Todorova, Tanya K., Forster, Paul M., Sorensen, Lasse K., Fdez. Galvan, Ignacio, Lindh, Roland, Czerwinski, Kenneth R., and Sattelberger, Alfred P. Molecular and electronic structure of Re2Br4(PMe3)4. United States: N. p., 2016.
Web. doi:10.1021/acs.inorgchem.6b01052.
Johnstone, Erik V., Poineau, Frederic, Todorova, Tanya K., Forster, Paul M., Sorensen, Lasse K., Fdez. Galvan, Ignacio, Lindh, Roland, Czerwinski, Kenneth R., & Sattelberger, Alfred P. Molecular and electronic structure of Re2Br4(PMe3)4. United States. https://doi.org/10.1021/acs.inorgchem.6b01052
Johnstone, Erik V., Poineau, Frederic, Todorova, Tanya K., Forster, Paul M., Sorensen, Lasse K., Fdez. Galvan, Ignacio, Lindh, Roland, Czerwinski, Kenneth R., and Sattelberger, Alfred P. Thu .
"Molecular and electronic structure of Re2Br4(PMe3)4". United States. https://doi.org/10.1021/acs.inorgchem.6b01052. https://www.osti.gov/servlets/purl/1339564.
@article{osti_1339564,
title = {Molecular and electronic structure of Re2Br4(PMe3)4},
author = {Johnstone, Erik V. and Poineau, Frederic and Todorova, Tanya K. and Forster, Paul M. and Sorensen, Lasse K. and Fdez. Galvan, Ignacio and Lindh, Roland and Czerwinski, Kenneth R. and Sattelberger, Alfred P.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.6b01052},
journal = {Inorganic Chemistry},
number = 14,
volume = 55,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2016},
month = {Thu Jul 07 00:00:00 EDT 2016}
}
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Works referenced in this record:
Multiple Bonds Between Metal Atoms
book, January 2005
- Cotton, F. Albert; Murillo, Carlos A.; Walton, Richard A.
Complex halides of the transition metals. XVIII. Reduction of the octahalodirhenate(III) anions by tertiary phosphines. Redox behavior of rhenium halides. VII. New class of metal-metal bonded dimers
journal, August 1975
- Ebner, J. R.; Walton, R. A.
- Inorganic Chemistry, Vol. 14, Issue 8
Experimental characterization of an electron-rich (.sigma.2.pi.4.delta.2.delta.*2) metal-metal triple bond. Synthesis, reactivity, and photoelectron spectral studies of trimethylphosphine complexes of dirhenium(II)
journal, March 1986
- Root, Dawn R.; Blevins, Charles H.; Lichtenberger, Dennis L.
- Journal of the American Chemical Society, Vol. 108, Issue 5
Complex halides of the transition metals. 26. Reactions of the octachlorodirhenate(III) anion with sodium borohydride in the presence of tertiary phosphines. Facile routes to the dimers Re2Cl4(PR3)4 and Re2H8(PR3)4
journal, September 1978
- Brant, P.; Walton, R. A.
- Inorganic Chemistry, Vol. 17, Issue 9
Metal carboxylates. 14. Reactions of molybdenum(II) and rhenium(III) carboxylates with gaseous hydrogen halides in alcoholic media. Synthesis, characterization, and reactivity of haloanions of molybdenum and rhenium, hexabromodimolybdate(1-), undecaiodotetramolybdate(2-), and octaiododirhenate(2-)
journal, November 1978
- Glicksman, H. D.; Walton, R. A.
- Inorganic Chemistry, Vol. 17, Issue 11
Mixed halide/phosphine complexes of the dirhenium core. Part 7. Reactions of [Re2I8]2− with monodentate phosphines
journal, April 2001
- Angaridis, Panagiotis; Cotton, F. Albert; Dikarev, Evgeny V.
- Polyhedron, Vol. 20, Issue 9-10
Molecular orbital and spectroscopic studies of triple bonds between transition-metal atoms. 2. The d5-d5 Re2Cl4(PR3)4 compounds
journal, May 1983
- Bursten, Bruce E.; Cotton, F. Albert; Fanwick, Phillip E.
- Journal of the American Chemical Society, Vol. 105, Issue 9
Magnetic and electrochemical properties of transition metal complexes with multiple metal-to-metal bonds. V. Tetrabenzoatodirhenium(n+) ion with n = 1 and 2, and tetrachlorotetrakis(triethylphosphine)dirhenium(n+) ion with n = 0, 1, and 2
journal, January 1975
- Cotton, F. Albert; Pedersen, Erik
- Journal of the American Chemical Society, Vol. 97, Issue 2
Electrochemical oxidations of complexes of rhenium(II) containing metal-metal triple bonds. Synthesis and characterization of paramagnetic cations of the type [Re2X4(PR3)4]+, where X = chlorine or bromine, possessing metal-metal bonds of order 3.5
journal, July 1978
- Brant, Patrick; Salmon, Dennis J.; Walton, Richard A.
- Journal of the American Chemical Society, Vol. 100, Issue 14
Heterogeneous electron-transfer kinetics for some multiply bonded dirhenium complexes
journal, December 1985
- Conner, Kay A.; Gennett, Thomas; Weaver, Michael J.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 196, Issue 1
Synthesis and structural characterization of bis[bis(dimethylphenylphosphine)dichlororhenium](n+) ion (n = 0-2): a series of complexes processing metal-metal bond orders of 4, 3.5, and 3 and the dependence of bond length upon bond order
journal, July 1983
- Cotton, F. Albert; Dunbar, Kim R.; Falvello, Larry R.
- Journal of the American Chemical Society, Vol. 105, Issue 15
Magnetic Circular Dichroism and Electronic Structure of [Re 2 X 4 (PMe 3 ) 4 ] + (X = Cl, Br)
journal, January 2014
- Habel-Rodriguez, Diana; Poineau, Frederic; Johnstone, Erik V.
- Inorganic Chemistry, Vol. 53, Issue 3
Structural studies on rhenium and tungsten halo trialkylphosphine, M2X4(PR3)4 compounds (M = rhenium, tungsten; X = Cl, Br; R = Me, n-Pr, n-Bu). The first examples of simple three-way disorder of dimetal units within ordered ligand cages
journal, October 1990
- Cotton, F. Albert; Jennings, J. Gregory; Price, Andrew C.
- Inorganic Chemistry, Vol. 29, Issue 20
Structural, Spectroscopic, and Multiconfigurational Quantum Chemical Investigations of the Electron-Rich Metal−Metal Triple-Bonded Tc 2 X 4 (PMe 3 ) 4 (X = Cl, Br) Complexes
journal, July 2010
- Poineau, Frederic; Forster, Paul M.; Todorova, Tanya K.
- Inorganic Chemistry, Vol. 49, Issue 14
Synthesis, structure, and first-principles calculations of [TcBr2(PMe3)4] and [Tc2Br4(PMe3)4] complexes
journal, January 2009
- Poineau, Frederic; Weck, Philippe F.; Forster, Paul M.
- Dalton Transactions, Issue 46
Some Reactions of the Octahalodirhenium(III) Ions. Reactions with Phosphines
journal, December 1965
- Cotton, F. A.; Curtis, N. F.; Robinson, W. R.
- Inorganic Chemistry, Vol. 4, Issue 12
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980
- Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M.
- Chemical Physics, Vol. 48, Issue 2
Second‐order perturbation theory with a complete active space self‐consistent field reference function
journal, January 1992
- Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O.
- The Journal of Chemical Physics, Vol. 96, Issue 2
The multi-state CASPT2 method
journal, May 1998
- Finley, James; Malmqvist, Per-Åke; Roos, Björn O.
- Chemical Physics Letters, Vol. 288, Issue 2-4
Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 110, Issue 13
Electronic structure calculations on workstation computers: The program system turbomole
journal, October 1989
- Ahlrichs, Reinhart; Bär, Michael; Häser, Marco
- Chemical Physics Letters, Vol. 162, Issue 3
MOLCAS 7: The Next Generation
journal, January 2010
- Aquilante, Francesco; De Vico, Luca; Ferré, Nicolas
- Journal of Computational Chemistry, Vol. 31, Issue 1
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set
December 2003
- Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke
New Relativistic ANO Basis Sets for Transition Metal Atoms
journal, July 2005
- Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke
- The Journal of Physical Chemistry A, Vol. 109, Issue 29
Calculation of transition density matrices by nonunitary orbital transformations
journal, October 1986
- Malmqvist, Per �ke
- International Journal of Quantum Chemistry, Vol. 30, Issue 4
The CASSCF state interaction method
journal, February 1989
- Malmqvist, Per-Åke; Roos, Björn O.
- Chemical Physics Letters, Vol. 155, Issue 2
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015
- Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
- Journal of Computational Chemistry, Vol. 37, Issue 5
Cholesky Decomposition-Based Multiconfiguration Second-Order Perturbation Theory (CD-CASPT2): Application to the Spin-State Energetics of Co III (diiminato)(NPh)
journal, April 2008
- Aquilante, Francesco; Malmqvist, Per-Åke; Pedersen, Thomas Bondo
- Journal of Chemical Theory and Computation, Vol. 4, Issue 5
Accurate ab initio density fitting for multiconfigurational self-consistent field methods
journal, July 2008
- Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland
- The Journal of Chemical Physics, Vol. 129, Issue 2
Atomic Cholesky decompositions: A route to unbiased auxiliary basis sets for density fitting approximation with tunable accuracy and efficiency
journal, April 2009
- Aquilante, Francesco; Gagliardi, Laura; Pedersen, Thomas Bondo
- The Journal of Chemical Physics, Vol. 130, Issue 15
Low-cost evaluation of the exchange Fock matrix from Cholesky and density fitting representations of the electron repulsion integrals
journal, May 2007
- Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland
- The Journal of Chemical Physics, Vol. 126, Issue 19
Luscus: molecular viewer and editor for MOLCAS
journal, April 2015
- Kovačević, Goran; Veryazov, Valera
- Journal of Cheminformatics, Vol. 7, Issue 1
Metal-Metal Multiply Bonded Complexes of Technetium. 1. Synthesis and Structural Characterization of Phosphine Complexes That Contain a Tc-Tc Multiple Bond
journal, May 1994
- Burns, Carol J.; Burrell, Anthony K.; Cotton, F. Albert
- Inorganic Chemistry, Vol. 33, Issue 10
Ligand perturbation of the molecular and electronic structures of quadruply bonded dimers. The crystal structures of Mo2Br4(PMe3)4 and Mo2I4(PMe3)4, and the vibrational and electronic spectra of a series of M2X4L4 complexes
journal, January 1987
- Hopkins, Michael D.; Schaefer, William P.; Bronikowski, Michael J.
- Journal of the American Chemical Society, Vol. 109, Issue 2
Molecular and electronic structures of two quadruply bonded ditungsten compounds and a dimolybdenum homolog
journal, July 1981
- Cotton, F. Albert; Extine, Michael W.; Felthouse, Timothy R.
- Journal of the American Chemical Society, Vol. 103, Issue 14
Single-crystal polarized spectra for the .delta. .fwdarw. .delta.* band of tetrabutylammonium octachlorodirhenate(III) and tetrabutylammonium octabromodihenate(III). Crystal structure of the octabromo salt
journal, January 1985
- Huang, Hei Wai; Martin, Don S.
- Inorganic Chemistry, Vol. 24, Issue 1
Crystal structure of octabromoditechnetate(iii) and a multi-configurational quantum chemical study of the δ→δ* transition in quadruply bonded [M2X8]2− dimers (M = Tc, Re; X = Cl, Br)
journal, January 2009
- Poineau, Frederic; Gagliardi, Laura; Forster, Paul M.
- Dalton Transactions, Issue 30
Mo2F4(PR3)4 compounds and a comparison of their properties with those of other Mo2X4(PR3)4 compounds. A new synthetic route to metal fluorides by the reaction of alkyl species with Olah's reagent
journal, March 1992
- Cotton, F. Albert; Wiesinger, Kenneth J.
- Inorganic Chemistry, Vol. 31, Issue 5