Open AccessThe oxidation of dimethyl sulphide, trimethylamine, and trimethylphosphine by solvated copper(II) or thallium(III) hexafluorometallates in acetonitrile
Author(s) -
Rana M. Siddique,
John M. Winfield
Publication year - 1989
Publication title -
canadian journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.323
H-Index - 68
eISSN - 1480-3291
pISSN - 0008-4042
DOI - 10.1139/v89-275
Subject(s) - chemistry , acetonitrile , hexafluorophosphate , thallium , trimethylphosphine , copper , trimethylamine , inorganic chemistry , redox , medicinal chemistry , organic chemistry , catalysis , molecule , ionic liquid
Dimethyl sulphide, trimethylamine, and trimethylphosphine are oxidized by solvated copper(II) hexafluorophosphate or solvated thallium(III) hexafluorouranate(V) in acetonitrile at room temperature. The reactions are all very similar and spectroscopic studies suggest that the oxidized products are the dinuclear, non-metal cations [Me 2 SSMe] + , [Me 3 NNMe 2 ] + , and [Me 3 PPMe 3 ] 2+ . The compound [Me 3 PPMe 3 ][PF 6 ] 2 is obtained from the oxidation of PMe 3 by diiodine in MeCN, followed by treatment with nitrosonium hexafluorophosphate. Coloured intermediates observed in the reactions of solvated Cu II are formulated as redox-active cations [CuL x (NCMe) y ] 2+ , L = SMe 2 , NMe 3 , or PMe 3 , and a generalized reaction scheme is proposed. Keywords: copper(II), thallium(III), acetonitrile, oxidation, fluorometallate.