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Title: Uncovering Multiple Metal-Metal Bonding in a Tetranuclear Fluoride Rhenium Cluster or the Curious Case of {[Ni(H2O)6](NH4)4}[Re4F18]·4H2O

Journal Article · · European Journal of Inorganic Chemistry
 [1];  [1];  [2];  [3];  [2];  [4]; ORCiD logo [1]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Freie Univ. Berlin (Germany)
  3. Technical Univ. of Munich, Garching (Germany). Catalysis Research Center
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
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The compound {[Ni(H2O)6](NH4)4}[Re4F18]·4H2O (1) has been isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy and computational methods. The compound 1 crystallizes in the triclinic space group P1 (a = 6.6620(9) Å, b = 9.7121(13) Å, c = 11.2007(15) Å, α = 67.644(2)°, β = 83.827(2)°, γ = 84.366(2)°). In 1, the [Re4F18]6– anion is composed of four Re(III) atoms bridged by two µ-bridging fluorine atoms and two di-µ-bridging fluorine atoms. Furthermore, in [Re4F18]6–, the shortest Re–Re distance (i.e., 2.3631(6) Å) is characteristic of the presence of a Re=Re double bond; the Re–F distances range from 1.854(6) to 2.008(5) Å. Theoretical calculations confirm the presence of a weak Re=Re double bond; the Mayer–Mulliken bond order of the doubly bridged Re atoms is 1.8097 and the natural localized molecular orbital bond order is 1.8751. The Raman spectrum of 1 has been measured and shows a series of bands in the region 167–1449 cm–1 that have been attributed to Re–F and Ni–O stretches, Re4F18 ring breathing and NH4+ bending and libration modes.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC02-06CH11357; NA0003180; NA0000979
OSTI ID:
1767149
Alternate ID(s):
OSTI ID: 1569775
Journal Information:
European Journal of Inorganic Chemistry, Vol. 2019, Issue 38; ISSN 1434-1948
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

References (52)

Fluorokomplexe des vierwertigen Rheniums journal January 1956
Al, Ga and In heterometallic wheels and their by-products journal January 2007
The Mayer bond order as a tool in inorganic chemistry† journal January 2001
The Raman spectrum of ammonium metavanadate journal October 1989
Octahedral aqua fluoride rhenium cluster complexes K[Re6S8F3(H2O)3]·7H2O, H3O[Re6Se8F3(H2O)3]·7H2O and [Re6Q8F2(H2O)4]·12H2O (Q=S, Se): Synthesis and structure journal June 2007
New isomeric tetranuclear cluster anions Mo4Cl123-. Fragments of the (Mo6Cl8)Cl62- octahedral cluster anion journal April 1986
Molecular octahedral sulfido-bromide rhenium clusters: Synthesis and crystal structure of (PPh4)2[Re6S6Br8] ∗d CH3C6H5 and (PPh4)3[Re6S7Br7] journal April 1996
Photochromism, Electrical Properties, and Structural Investigations of a Series of Hydrated Methylviologen Halobismuthate Hybrids: Influence of the Anionic Oligomer Size and Iodide Doping on the Photoinduced Properties and on the Dehydration Process journal July 2010
Hydrogen atoms location in [Re4(µ3-H)4(CO)12] by joint X-ray single-crystal and neutron powder diffraction analysis journal January 1997
Electrochemical Synthesis, Structural Characterization, and Decomposition of Rhenium Oxoethoxide, Re 4 O 4 (OEt) 12 . Ligand Influence on the Structure and Bonding in the High-Valent Tetranuclear Planar Rhenium Alkoxide Clusters journal February 2008
Density functional theory for transition metals and transition metal chemistry journal January 2009
Molecular and Electronic Structures of M 2 O 7 (M = Mn, Tc, Re) journal February 2017
LOBA: a localized orbital bonding analysis to calculate oxidation states, with application to a model water oxidation catalyst journal January 2009
The prediction of Raman spectra by density functional theory. Preliminary findings journal December 1995
Synthesis and structural characterization of three new platinum(IV) halide anions as triphenylcarbenium salts. Isolation from reaction of platinum tetrachloride with trityl chloride in benzene of a novel [Pt4(C6H4)2Cl14]2- anion containing o-phenylene ligands journal July 1972
The anomeric effect with central atoms other than carbon. 2. Strong interactions between nonbonded substituents in mono- and polyfluorinated first- and second-row amines, FnAHmNH2 journal November 1988
Non-bonding molecular orbitals and the chemistry of non-classical organic molecules journal January 1994
Chemical bonding in hypervalent molecules. The dominance of ionic bonding and negative hyperconjugation over d-orbital participation journal February 1990
Infrared absorption spectra of aquo complexes and the nature of co-ordination bonds journal March 1964
Notizen: Synthese und Eigenschaften des Oktafluorodirhenat(III) -anions, [Re2F8]2- / Synthesis and Properties of the Octafluorodirhenate(III) Anion, [Re2F8]2- journal December 1979
Metal ion directed self-assembly of sensors for ions, molecules and biomolecules journal January 2011
Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes journal December 2017
Syntheses, Raman spectroscopy and crystal structures of alkali hexafluoridorhenates(IV) revisited journal April 2018
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Ditechnetium Heptoxide Revisited: Solid-State, Gas-Phase, and Theoretical Studies journal September 2016
Syntheses and Characterizations of the New Tetranuclear Rhenium Cluster Compounds Re 4 (μ 3 -Q) 4 (TeCl 2 ) 4 Cl 8 (Q = S, Se, Te) journal February 1997
Crystal and molecular structure of trirhenium nonaiodide journal August 1968
The Crystal Structure of Cesium Dodecachlorotrirhenate-(III), a Compound with a New Type of Metal Atom Cluster journal December 1963
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
A short history of SHELX journal December 2007
High-yield synthesis of the cuboidal rhenium cluster [Re4S4(CN)12]4− by reaction of the triangular cluster [Re3S7Br6]+ with cyanide journal February 1996
Rhenium Fluorides journal October 1980
Octahedral clusters of rhenium tellurobromide: Syntheses and crystal structures of [NPr4]2[Re6Te6Br8] and [PPh4][Re6Te5Br9] journal July 1998
The Metal-Metal Bonded, Polynuclear Complex Anion in CsReCl 4 journal May 1963
First Examples of Chalcofluoride Rhenium Cluster Complexes with Cubane-Like Anions [Re4Q4F12]4- (Q = S, Se) journal June 2005
Measurement of the Raman spectrum of liquid water journal February 1998
Natural hybrid orbitals journal September 1980
Compounds Containing Dirheniurm(III) Octahalide Anions journal March 1965
Self-assembled tetranuclear metallacyclic chair using orthogonal tritopic acceptors, angular ditopic donors, and bischelating bridging motifs journal February 2011
Raman scattering from NH 4 + and ND 4 + in beta‐alumina journal August 1980
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Octafluorodirhenate(III) Revisited: Solid-State Preparation, Characterization, and Multiconfigurational Quantum Chemical Calculations journal May 2016
[2 + 2] Cycloaddition of rhenium-rhenium quadruple bonds. Structural characterization of the first cyclotetrarhenium diynes, (n-Bu4N)2Re4Cl8(.mu.-O)2(.mu.-OMe)(.mu.-X) (X = Cl or OMe) journal July 1991
Structural and dielectric properties of thiazolium chlorobismuthate(III) and chloroantimonate(III) journal September 2008
A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions journal May 1989
Energy-adjustedab initio pseudopotentials for the second and third row transition elements journal January 1990
A new rectangular Re4 cluster compound of the metallocyclodiyne Type journal September 1995
Raman spectroscopy of the ammonium ion in NH 4 MnF 3 and NH 4 ZnF 3 perovskites: temperature dependence journal March 1988
[ReF 6 ] 2− : A Robust Module for the Design of Molecule-Based Magnetic Materials journal January 2014
Crystal structure of the tellurocyanide cluster complex K4[Re4Te4(CN)12]·5H2O journal March 1999
Crystal structure of bis(dimethylammonium) hexaaquanickel(II) bis(sulfate) dihydrate journal October 2014
Hydrothermal chemistry of oligomeric vanadium oxyfluorides journal January 2007

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
rhenium fluoride cluster
metal-metal bonding
rhenium
fluorine
cluster compounds
structure elucidation