Co-ordination Chemistry of Higher Oxidation States. Part 22. trans-Dioxo-osmium(VI) Complexes of Diamines, Diphosphines, and Diarsines

DOI: 10.1039/DT9870000633

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Journal of the Chemical Society, Dalton Transactions p. 633 - 638 (1987)

Update date:2022-08-05

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Authors:

Harbron, Stephen K.

Levason, William

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Article abstract of DOI:10.1039/DT9870000633

The reactions of tertiary arsines and diarsines with a mixture of OsO4, concentrated HCl, and ethanol at low temperatures produce the dioxo-osmium(VI) complexes (L=AsEt3, AsMe2Ph, or AsPh3) and .The corresponding reactions at higher temperatures lead to mixtures containing Os^IV complexes and chloro complexes of Os^III and Os^IV.The diphosphine complexes are prepared similarly, but are very difficult to obtain pure, and the bromo complexes (L-L)= diphosphine or diarsine> are obtained from OsO4, concentrated HBr, EtOH, and L-L.NNN'N'-Tetramethylenediamine (tmen) produces , and has been characterised as a minor by-product in the case of X=Cl.Bis-ligand complexes have been characterised by i.r., u.v.-visible, (1)H, and (31)P n.m.r. spectroscopy and microanalysis.Decomposition in solution is suggested to involve oxygen-atom transfer from the OsO2(2+) group to the neutral ligand.The properties and stabilities of the complexes are discussed and the ease of oxidation of the neutral ligands is suggested to be a major factor determining relative stabilities.

Full text of DOI:10.1039/DT9870000633

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