Abstract
Exposure of solutions of triphenyl-phosphine and -arsine in sulphuric acid at 77 K to 60Co γ-rays gave the corresponding cations, characterised by their e.s.r. spectra. Triphenylphosphine oxide, sulphide, and selenide also gave Ph3P˙+ radicals together with species thought to be Ph3ṖSH and Ph3ṖSeH from the sulphide and selenide. These species are thought to have a near tetrahedral, σ*, structure rather than the ‘normal’ trigonal bipyramidal structure. Diphenylmethyl- and phenyldimethyl-phosphine gave cations with e.s.r. parameters between the extremes for Ph3P˙+ and Me3P˙+. Triphenylarsine oxide in sulphuric acid also gave Ph3 As˙+, but in methanol either Ph3ȦsO– or Ph3ȦsOR was formed. Tetraphenylarsonium cations in methanolic solution at 77 K gave Ph4 As˙ but no such species was obtained from tetraphenylphosphinium cations. From these results various modes of electron addition to the parent compounds are deduced and discussed.
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Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
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