Electronic Properties of Thiolate Compounds of Oxomolybdenum (V) and their Tungsten and Selenium Analogues. Effects of 17-O, 98-Mo and 95-Mo Isotope Substitution upon ESR Spectra

Hanson, Graeme R., Brunette, Andrew A., McDonell, Angus C., Murray, Keith S. and Wedd, Anthony G. (1981) Electronic Properties of Thiolate Compounds of Oxomolybdenum (V) and their Tungsten and Selenium Analogues. Effects of 17-O, 98-Mo and 95-Mo Isotope Substitution upon ESR Spectra. Journal of the American Chemical Society, 103 8: 1953-1959.


Author Hanson, Graeme R.
Brunette, Andrew A.
McDonell, Angus C.
Murray, Keith S.
Wedd, Anthony G.
Title Electronic Properties of Thiolate Compounds of Oxomolybdenum (V) and their Tungsten and Selenium Analogues. Effects of 17-O, 98-Mo and 95-Mo Isotope Substitution upon ESR Spectra
Formatted title Electronic Properties of Thiolate Compounds of Oxomolybdenum (V) and their Tungsten and Selenium Analogues. Effects of 17O, 98Mo and 95Mo Isotope Substitution upon ESR Spectra
Journal name Journal of the American Chemical Society   Check publisher's open access policy
Publication date 1981-04
Sub-type Article
DOI 10.1021/ja00398a013
Volume number 103
Issue number 8
ISSN 0002-7863
Start page 1953
End page 1959
Total pages 7
Place of publication Washington, D.C. U.S.A.
Publisher American Chemical Society
Language eng
Subject 030201 Bioinorganic Chemistry
030606 Structural Chemistry and Spectroscopy
Formatted abstract The series of crystalline, mononuclear B+[MO(XR)4]- and triply bridged binuclear B+[M2O2(XR)6(OMe)]- (M = Mo, W; X = S, Se; R = aryl; B = quaternary cation) salts have been isolated and the anions [MoO(SR)4]- (R = Et, CH2Ph) stabilized in solution at -60°C. The mononuclear anions are intensely colored due to a ligand-to-metal charge-transfer transition which is absent in the binuclear species. The magnetic susceptibilities of (Et4N)[MO(SPh)4] show a Curie dependence in the range 300-4.2 K with minor deviations in the tungsten compound. The behavior is essentially that of magnetically dilute 4d1 and 5d1 systems exhibiting a tetragonal ligand field and greatly reduced spin-orbit coupling on the metal. The presence of strong spin-spin coupling in the binuclear compounds leads to magnetic moments close to 0. ESR spectra (at X- and Q-band frequencies) of the mononuclear anions exhibit axial symmetry, and 98Mo and 95Mo isotope substitution and computer simulation permit accurate extraction of the g and hyperfine tensor anisotropies. Exceptionally narrow line widths permit observation of 17O-superhyperfine coupling in 17O-enriched [98MoO(SPh)4]- (a = 2.2 × 10-4 cm-1). © 1981 American Chemical Society.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article
Collection: Centre for Advanced Imaging Publications
 
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