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Resonance Raman Spectra of [M(6)X(8)Y(6)](2)(-) Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)
Authors:Schoonover Jon R  Zietlow Thomas C  Clark David L  Heppert Joseph A  Chisholm Malcolm H  Gray Harry B  Sattelberger Alfred P  Woodruff William H
Institution:Chemical Science and Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545.
Abstract:Resonance Raman spectra of the cubic metal-halide complexes having the general formula M(6)X(8)Y(6)](2)(-) (M = Mo or W; X, Y = Cl, Br, or I) are reported. The three totally symmetric fundamental vibrations of these complexes are identified. The extensive mixing of the symmetry coordinates that compose the symmetric normal modes expected in these systems is not observed. Instead the "group-frequency" approximation is valid. Furthermore, the force constants of both the apical and face-bridging metal-halide bonds are insensitive to the identity of either the metal or the halide. Raman spectra of related complexes with methoxy and benzenethiol groups as ligands are reported along with the structural data for Mo(6)Cl(8)(SPh)(6)]NBu(4)](2). Crystal data for Mo(6)Cl(8)(SPh)(6)]NBu(4)](2) at -156 degrees C: monoclinic space group P2(1)/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) ?; beta = 118.53(1) degrees, V = 3223.4 ?(3); d(calcd) = 1.664 g cm(-)(3); Z = 2.
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