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Low-temperature neutron diffraction analysis of (Rh/sub 4/(eta/sup 5/-C/sub 5/Me/sub 5/)/sub 4/H/sub 4/)(BF/sub 4/)/sub 2/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00181a010· OSTI ID:6139926
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A low-temperature (12 K) neutron diffraction study of (Rh/sub 4/(eta/sup 5/-C/sub 5/Me/sub 5/)/sub 4/H/sub 4/)(BF/sub 4/)/sub 2/ has been performed to determine whether the hydride ligands bridge the edges or faces of the tetranuclear rhodium cluster. Both anions and cations lie on sites of 4-S/sub 4/ symmetry. The cation is a stable, 58-electron, diamagnetic complex consisting of a tetrarhodium cluster with a C/sub 5/Me/sub 5/ ligand attached to each metal. The Rh/sub 4/ core shows substantial distortion from a regular tetrahedron, resulting in four long and two short Rh-Rh distances. The hydrides were found to bridge the faces of the tetrarhodium cluster at a distance of 0.96 A above the planes formed by three Rh atoms. The Rh-Rh distances are 2.610 (5) and 2.829 (5) A, and the Rh atoms are 1.84 A from the C/sub 5/-ring planes. A detailed /sup 1/H and /sup 13/C NMR analysis establishes that the hydride ligands also are face bridging in solution. Calculations based on idealized tetrahedral geometry for the molecular framework show no abnormally short nonbonded contacts, and thus distortion from T/sub d/ symmetry appears to be electronic rather than steric in origin. Crystallographic data for (C/sub 40/H/sub 64/Rh/sub 4/)(BF/sub 4/)/sub 2/: tetragonal, space group Ianti 4, Z = 2, a = 11.459 (3) A, c = 15.481 (8) A, R(F/sup 2/) = 0.069 for 1371 reflections with (sin theta)/lambda < 0.83 A/sup -1/. 22 references, 4 figures, 4 tables.

Research Organization:
Brookhaven National Lab., Upton, NY
OSTI ID:
6139926
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:13; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
BOND ANGLE
BORON COMPOUNDS
BORON FLUORIDES
COHERENT SCATTERING
COMPLEXES
CORRELATIONS
CRYSTALLOGRAPHY
DATA
DIENES
DIFFRACTION
DISTANCE
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INTERATOMIC DISTANCES
LIGANDS
MATHEMATICAL MODELS
MATHEMATICS
MOLECULAR STRUCTURE
NEUTRON DIFFRACTION
NMR SPECTRA
NUMERICAL ANALYSIS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
REFRACTORY METAL COMPOUNDS
RHODIUM COMPLEXES
RHODIUM COMPOUNDS
RHODIUM HYDRIDES
SCATTERING
SPECTRA
STABILITY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VERY LOW TEMPERATURE