- Redox Chemistry of the Homoleptic Aryl Os(2-MeC6H4)4: Synthesis and Characterization of the First Osmium(v) Organometallic
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Oxidation of Os(2-MeC6H4)4 in CH2Cl2 gives the remarkably stable osmum(v)tetra-aryl salts, , (Y=BF4-, CF3SO3-); the triflate salt has been characterized by X-ray crystallography.
- Arnold, John,Wilkinson, Geoffrey,Hussain, Bilquis,Hursthouse, Michael B.
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- Synthesis and molecular structures of monooxo aryl complexes of osmium(VI)
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Reaction of [OsO4] with C7H7MgBr (C7H7 = 2-methylphenyl) followed by column chromatography afforded the reported osmium tetraaryl [Os(C7H7)4] along with the oxo-osmium(VI) ([OsO(C7H7)4]) (1) (13%) and the dioxoosmium(VI) ([OsO2(C7H7)2]) (2) (25%) complexes. Treatment of [OsO4] with C8H9MgBr (C8H9 = 2,5-dimethylphenyl) gave a mixture of [Os(C8H9)4] (3) (34%) and [OsO(C8H9)4] (4) (4%) while that with C8H9OMgBr (C8H9O = 4-methoxy-2-methylphenyl) afforded [OsO(C8H9O)4] (5) in 20% yield. Oxidation of 3 with 3-chloroperoxybenzoic acid afforded 4 in good yield. The solid-state structures of 1 and 4 have been established by X-ray crystallography. Crystals of 1 are tetragonal with a = 13.080(1) and c = 6.6506(5) A, V = 1137.9(1) A3, Z = 2, and space group of P4/n; while those of 4 are tetragonal with a = 13.593(2) and c = 7.377(2) A, V = 1363.0(5) A3, Z = 4, and space group of P4/n. The geometry around osmium in both complexes is square pyramidal with the oxo ligand occupying apical position. The Os - O and Os - C distances in 1 are 1.652(2) and 2.084(1) A, respectively, while those in 4 are 1.688(7) and 2.088(4) A, respectively. The cyclic voltammograms of the monooxo aryl osmium(VI) compounds show reversible Os(VI/V) couple at around -1.4 V vs. ferrocene/ferrocenium couple.
- Lau,Chim,Wong,Williams,Leung
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p. 607 - 612
(2007/10/03)
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- Mechanistic studies of ligand-induced thermolytic reductive elimination of biaryl from tetraarylosmium(IV)
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The reaction of new tetraarylosmium(IV) complexes Os(2,4-Me2C6H3)4 and Os(4-F-2-MeC6H3)4 with PMe3 and P(OMe)3 has been investigated, as have the reactions between Os(
- Hardy, David T.,Wilkinson, Geoffrey,Young, G. Brent
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p. 1363 - 1373
(2008/10/09)
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- Synthesis and X-Ray Crystal Structure of Tetra(2-methylphenyl)molybdenum(IV), Mo(2-MeC6H4)4. Redox Chemistry of M(2-MeC6H4)4 Compounds of Molybdenum, Rhenium, Ruthenium, and Osmium
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The reaction of MoCl4(thf)2 (thf = tetrahydrofuran) with 4 equivalents of o-tolyl-lithium in diethyl ether yields Mo(2-MeC6H4)4 as air-sensitive purple crystals, characterized by X-ray crystallography.The redox chemistry of M(2-MeC6H4)4 (M = Mo, Re, Ru, or Os) has been studied by cyclic voltammetry and chemical methods.One-electron oxidation of the ruthenium and osmium derivatives gives tetra-aryl cations (1+); the osmium complex crystallizes from dichloromethane-diethyl ether as BF4(1-) or CF3SO3(1-) salts which have been fully characterized.
- Arnold, John,Wilkinson, Geoffrey,Hussain, Bilquis,Hursthouse, Michael B.
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p. 2149 - 2154
(2007/10/02)
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- The Synthesis and X-Ray Crystal Structures of Homoleptic Tetrahedral Aryls of Osmium(IV) and of Cyclohexyls of Ruthenium(IV), Osmium(IV), and Chromium(IV)
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The interactions of o-tolylmagnesium bromide or AlPh3(OEt2) with osmium tetraoxide leads to the isolation of the homoleptic, tetrahedral osmium(IV) compounds OsR4 (R = C6H4Me-o or C6H5).Thermally stable M(C6H11)4 compounds (M = Ru, Os, or Cr; C6H11 = cycl
- Stavropoulos, Pericles,Savage, Paul D.,Tooze, Robert P.,Wilkinson, Geoffrey,Hussain, Bilquis,et al.
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p. 557 - 562
(2007/10/02)
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