
TY  - JOUR
A1  - Bayston, JH 
A1  - Looney, FD 
A1  - Winfield, ME 
T1  - Paramagnetic Products of the Oxidation of Cyanocobaltate(II)
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1963
VL  - 16
IS  - 4
SP  - 557
EP  - 564
KW  - 
UR  - https://doi.org/10.1071/CH9630557 
N2  - By means of a low-temperature ESR technique, several paramagnetic complexes have been detected during the reaction of aqueous [CoII(CN)5]3- with O2. Of these only [(CN)5CoIII-O-O-CoIV(CN)5]5-, the final oxidation product, is stable in solution. It has a 15-line spectrum resembling that of [(NH3)5CoIII-O-O-CoIV(NH3)5]5+ but more sharply defined and independent of pH.   Under very alkaline conditions the first oxidation product detectable by ESR has an 8-line signal, indicating a mononuclear complex, possibly [(CN)5CoIII-O-O]3-. It is an intermediate in the oxidation of [(CN)5CoIII-O-O-CoIII(CN)5]6- to [(CN)5CoIII-O-O-CoIV(CN)5]5- and may reach a high concentration in the presence of 0.5M KOH. Although it may also prove to be the expected mononuclear inter- mediate in the oxidation of [CoII(CN)5]3- to [(CN)5CoIII-O-O-CoIII(CN)5]6-, no 8-line signal is detected until the cyanocobaltate(II) has been consumed.  Present in small amount is a mononuclear complex with 16 lines, apparently a by-product. Larger amounts can be formed by reducing [(CN)5CoIII-O-O-CoIII(CN)5]6- with NaBH4 in strong alkali at -20°C. 
ER  -

