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• W2153621219 endingPage "2487" @default.
• W2153621219 startingPage "2487" @default.
• W2153621219 abstract "The highly unusual Mo(VI) thioether complexes [MoO2X2(L–L)] (X = Cl or Br; L–L = MeS(CH2)2SMe or EtS(CH2)2SEt) were obtained by reaction of MoO2X2 with L–L in rigorously anhydrous CH2Cl2 solution. Similar reaction of MoO2Cl2 with the diselenoether MeSe(CH2)2SeMe gives the very reactive [MoO2Cl2{MeSe(CH2)2SeMe}] as a yellow solid. These compounds are very moisture sensitive and were characterised by IR, diffuse reflectance UV-vis and multinuclear (1H, 13C{1H}, 77Se and 95Mo) NMR spectroscopy. The data are consistent with distorted 6-coordination at Mo(VI) viatrans X ligands, mutually cis oxo groups and a chelating dithio- or diseleno-ether ligand. Variable temperature 1H and 13C{1H} NMR data indicate fast pyramidal inversion at the coordinated chalcogen atoms occurs at room temperature, but cooling slows this process to reveal resonances consistent with the meso and DL forms. The 95Mo NMR spectra are single resonances in the region 200–300 ppm, as expected for Mo(VI) complexes, and show inverse dependence of the chemical shifts upon both halide and chalcogen type. Crystal structures of three of the dithioether complexes are described and provide unequivocal evidence for Mo(VI) thioether coordination, confirming chelation of the dithioether through long Mo–S interactions of ca. 2.7 Å. Attempts to extend the range of compounds by using other chalcogenoether ligands failed, indicating that to obtain complexes involving these extremely mis-matched metal ligand combinations requires both the favourable 5-membered chelate ring and small terminal alkyl substituents on the chalcogen." @default.
• W2153621219 created "2016-06-24" @default.
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• W2153621219 date "2004-01-01" @default.
• W2153621219 modified "2023-10-11" @default.
• W2153621219 title "Synthesis, spectroscopic and structural properties of hexavalent molybdenum complexes with thio- and seleno-ether ligands" @default.
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• W2153621219 doi "https://doi.org/10.1039/b406175f" @default.
• W2153621219 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/15303163" @default.
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