Detail of "15702-05-3"

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Coordination chemistry of higher oxidation states

Coordination chemistry of higher oxidation states. Part 38. Synthesis, spectroscopic and electrochemical studies of some trans-dihalogenoosmium complexes. Crystal structure of trans-[Os(PMe3)4Cl2]BF4. Champness, Neil R.; Levason, William; Mould, Roy A. S.; Pletcher, Derek; Webster, Michael (Dep. Chem., Univ. Southampton, Southampton SO9 5NH, UK). J. Chem. Soc., Dalton Trans., (10), 2777-83 (English) 1991. CODEN: JCDTBI. ISSN: 0300-9246. DOCUMENT TYPE: Journal CA Section: 78 (Inorganic Chemicals and Reactions) Section cross-reference(s): 72, 75 trans-[Os(PMe3)4X2] (X = Cl or Br) have been obtained from [Os(PPh3)3X2] and PMe3, and trans-[OsL4X2] [L = PMe2Ph, AsMe3, SbPh3, py] by redn. of appropriate osmium(III) complexes in the presence of L. cis-[Os(PR3)4X2] are formed by isomerization of the trans analogs in chlorinated solvents, and in other ways. Air oxidn. of the osmium(II) complexes gives trans-[OsL4X2]BF4 (L = PMe3 or AsMe3), but formation of trans-[OsL4X2]BF4 (L = PMe2Ph, SbPh3, py) and cis-[Os(PMe2Ph)4Cl2]BF4 requires HNO3 as oxidant. Use of concd. HNO3 gives trans-[OsL4X2]2+ (L = PMe3, PMe2Ph or AsMe3) in soln., but these have not been isolated. The complexes have been characterized by IR, UV-visible, and NMR spectroscopies, and the effect of stereochem. and L and X upon the OsII-OsIII and OsIII-OsIV redox potentials probed by cyclic voltammetry. The crystal structure of trans-[Os(PMe3)4Cl2]BF4 has been detd.: orthorhombic, space group Fddd, a 8.104(4), b 32.195(11), c 38.540(9) ?, Z = 16, R = 0.060, and R' = 0.053. The cation has Os-P 2.419(5) and 2.398(5) ? and Os-Cl 2.352(4) ?, and shows deviations of the OsP4 unit from planarity due to steric interactions. There is not evidence that mer-[IrL3Cl3] (L = PEtPh2, AsMe2Ph, SbPh3 or SMe2) can be oxidized either chem. or electrochem. to stable iridium(IV) cations.Except for chemicals metioned above, 15702-05-3 and 110682-49-0 are also used. .