Platinum cyanide radical

Yoshida has studied anodic oxidations in methanol containing cyanide to elucidate the electrode processes themselves.288 He finds that, under controlled potential ( 1.2 V), 2,5-dimethylfuran gives a methoxynitrile as well as a dimethoxy compound (Scheme 57). Cyanide competes for the primary cation radical but not for the secondary cations so that the product always contains at least one methoxy group. On a platinum electrode the cis-trans ratio in the methoxynitrile fraction is affected by the substrate concentration and by the addition of aromatic substances suggesting that adsorption on the electrode helps determine the stereochemistry. On a vitreous carbon electrode, which does not strongly adsorb aromatic species, the ratio always approaches the equilibrium value. 

Esr studies wth organic spin traps have shown that azide radicals (N3) are formed in the reaction of hydroxyl radicals with azide ions, and that the radicals N 3 and OCN are formed by persulfate oxidations of azide and cyanide. However, azide radicals could not be detected in the photochemical reductive cis elimination of cw-diazidobis(triphenylphosphine)platinum(II) to give Pt(PPh3)2, even though they have been observed in the esr spectra of the photolysis products of other azido complexes. It is suggested, therefore, that the azide ligands are cleaved off as Ne (hexaazabenzene). Calculations have shown that Ne is slightly stabilized and could therefore be stable at the low temperatures of these experiments. 

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