69609-04-7Relevant academic research and scientific papers
Triply bridged binuclear complexes of oxomolybdenum(V) with thiolate ligands
Buchanan, Iain,Clegg, William,Garner, C. David,Sheldrick, George M.
, p. 3657 - 3661 (2008/10/08)
Reaction of [MoOCl3(thf)2] with aromatic thiols HSAr (Ar = Ph or 4-MeC6H4) and sodium methoxide/methanol yields the complex ions [Mo2O2(SAr)6(OMe)]-, which have been obtained as crystalline [Et4N]+ salts. The structure of [Et4N][Mo2O2(4-MeC6H 4S)6(OMe)] has been determined by single-crystal X-ray diffraction. Crystals are orthorhombic, space group P21212, with a = 26.416 (4) ?, b = 41.380 (6) ?, c = 15.237 (2) ?, and Z = 12. Refinement, based on 7034 diffractometer data, gave R = 0.110. There are three crystallographically independent anions, each with two terminal oxo groups, four terminal and two bridging thiolate ligands, and a bridging methoxy ligand, arranged around a Mo2 center with Mo-Mo = 2.919 (5) ?.
Electronic Properties of Thiolate Compounds of Oxomolybdenum(V) and Their Tungsten and Selenium Analogues. Effects of 17O, 98Mo, and 95Mo Isotope Substution upon ESR Spectra
Hanson, Graeme R.,Brunette, Andrew A.,McDonell, Angus C.,Murray, Keith S.,Wedd, Anthony G.
, p. 1953 - 1959 (2007/10/02)
The series of crystalline, mononuclear B+- and triply bridged binuclear B+- (M = Mo, W; X = S, Se; R = aryl; B = quaternary cation) salts have been isolated and the anions - (R = Et, CH2Ph) stabilized in solution at -60 deg 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) 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 - (a = 22.2*10-4 cm-1).
