Resonance Raman Spectra of [M6X8Y6]2- Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)

Jon R. Schoonover; Thomas C. Zietlow; David L. Clark; Joseph A. Heppert; Malcolm H. Chisholm; Harry B. Gray; Alfred P. Sattelberger; William H. Woodruff

doi:10.1021/ic960184b

Resonance Raman Spectra of [M₆X₈Y₆]^2- Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)

Jon R. Schoonover, Thomas C. Zietlow, David L. Clark, Joseph A. Heppert, Malcolm H. Chisholm, Harry B. Gray, Alfred P. Sattelberger, William H. Woodruff

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Abstract

Resonance Raman spectra of the cubic metal-halide complexes having the general formula [M₆X₈Y₆]^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 [Mo₆Cl₈(SPh)₆][NBu₄]₂. Crystal data for [Mo₆Cl₈(SPh)₆] [NBu₄]₂ at -156 °C: monoclinic space group P2₁/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) Å; β= 118.53(1)°, V = 3223.4 Å³; d_calcd = 1.664 g cm^-3; Z = 2.

Original language	English
Pages (from-to)	6606-6613
Number of pages	8
Journal	Inorganic Chemistry
Volume	35
Issue number	22
DOIs	https://doi.org/10.1021/ic960184b
State	Published - 1996

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@article{2bd261df946a4ac5ab07e32dca684c2c,

title = "Resonance Raman Spectra of [M6X8Y6]2- Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)",

abstract = "Resonance Raman spectra of the cubic metal-halide complexes having the general formula [M6X8Y6]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 [Mo6Cl8(SPh)6][NBu4]2. Crystal data for [Mo6Cl8(SPh)6] [NBu4]2 at -156 °C: monoclinic space group P21/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) {\AA}; β= 118.53(1)°, V = 3223.4 {\AA}3; dcalcd = 1.664 g cm-3; Z = 2.",

author = "Schoonover, {Jon R.} and Zietlow, {Thomas C.} and Clark, {David L.} and Heppert, {Joseph A.} and Chisholm, {Malcolm H.} and Gray, {Harry B.} and Sattelberger, {Alfred P.} and Woodruff, {William H.}",

year = "1996",

doi = "10.1021/ic960184b",

language = "English",

volume = "35",

pages = "6606--6613",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

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T1 - Resonance Raman Spectra of [M6X8Y6]2- Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)

AU - Schoonover, Jon R.

AU - Zietlow, Thomas C.

AU - Clark, David L.

AU - Heppert, Joseph A.

AU - Chisholm, Malcolm H.

AU - Gray, Harry B.

AU - Sattelberger, Alfred P.

AU - Woodruff, William H.

PY - 1996

Y1 - 1996

N2 - Resonance Raman spectra of the cubic metal-halide complexes having the general formula [M6X8Y6]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 [Mo6Cl8(SPh)6][NBu4]2. Crystal data for [Mo6Cl8(SPh)6] [NBu4]2 at -156 °C: monoclinic space group P21/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) Å; β= 118.53(1)°, V = 3223.4 Å3; dcalcd = 1.664 g cm-3; Z = 2.

AB - Resonance Raman spectra of the cubic metal-halide complexes having the general formula [M6X8Y6]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 [Mo6Cl8(SPh)6][NBu4]2. Crystal data for [Mo6Cl8(SPh)6] [NBu4]2 at -156 °C: monoclinic space group P21/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) Å; β= 118.53(1)°, V = 3223.4 Å3; dcalcd = 1.664 g cm-3; Z = 2.

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U2 - 10.1021/ic960184b

DO - 10.1021/ic960184b

M3 - Article

AN - SCOPUS:0000152260

SN - 0020-1669

VL - 35

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

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Resonance Raman Spectra of [M₆X₈Y₆]^2- Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)

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