Resonance Raman Spectra of [M(6)X(8)Y(6)](2)(-) Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)

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) Å; beta = 118.53(1) degrees, V = 3223.4 Å(3); d(calcd) = 1.664 g cm(-)(3); Z = 2.