Inorganic Chemistry p. 2379 - 2382 (1978)
Update date:2022-07-30
Topics:
Salmon
Walton
The osmium(V) complex OsOCl3(PPh3)2, which was purported to be formed upon reacting osmium tetraoxide with triphenylphosphine and hydrochloric acid in refluxing ethanol, is shown to be a mixture of OsO2Cl2(PPh3)2 and trans-OsCl4(PPh3)2. This conclusion is supported by infrared and X-ray photoelectron spectroscopic (XPS) measurements and the isolation of analytically pure samples of the osmium(VI) and osmium(IV) complexes. The dicarbonyl complex Os(CO)2Cl2(PPh3)2 has also been isolated from the OsO4-PPh3-HCl reaction mixture in ethanol when long reflux periods (6-8 h) are used. The reaction of OsO2Cl2(PPh3)2 with refluxing pyridine produces the osmium(II) complex OsCl2(py)3(PPh3), while trans-OsCl4(PPh3)2 is reduced to the osmium(III) complexes OsCl3(py)2(PPh3) and OsCl3(PPh3)2(CH3CN) by pyridine and acetonitrile, respectively. These mixed-ligand complexes exhibit a rich redox chemistry as demonstrated by cyclic voltammetry.
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Doi:10.1002/jhet.5570400618
(2003)Doi:10.1021/ja00479a060
(1978)Doi:10.1021/jo9624004
(1997)Doi:10.1021/ma035289u
(2004)Doi:10.1016/j.bmc.2014.09.046
(2014)Doi:10.1002/jccs.200300127
(2003)
