The reaction of dipotassium hydridotetracyanoaquorhodate(III) with oxygen. Dipotassium hydroperoxotetracyanoaquorhodate(III)

Abstract

The reaction of the hydrido-complex [RhH(CN₄)(H₂O)]^2– with molecular oxygen has been investigated. The product we have obtained appears to be the hydroperoxo-complex, [Rh(O₂H)(CN)₄(H₂O)]^2– rather than the binuclear µ-peroxo-complex [(CN)₄(H₂O)Rh·O₂·Rh(H₂O)(CN)₄]^4– as has previously been reported. Acid hydrolysis yields the bisaquo-complex [Rh(CN)₄(H₂O)₂]^– and hydrogen peroxide. This complex is not readily reconverted to the hydride by the action of sodium borohydride. An improved method of preparation of the hydroperoxopentacyanocobaltate(III) complex, [Co(O₂H)(CN)₅]^3–, is reported as are some i.r. spectral data of these complexes.