Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Derivatographic Studies on Transition Metal Complexes. IX. Thermal CN-Bridging Reaction of Double Complex Salts in Solid Phase
Ryokichi TsuchiyaShigeo NakagawaAkira UeharaEishin Kyuno
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1973 Volume 46 Issue 1 Pages 169-175


It was found by derivatography and spectral measurements that the double complex salts, [Co(H2O)2N4] [Co(CN)6nH2O, where N4 is 4NH3, two moles of ethylenediamine (en) or one mole of triethylenetetramine (trien), [Co(NH3)2trien][Co(CN)6]·2H2O, [Co(NH3)tepa][Co(CN)6].2H2O, where tepa is tetraethylenepent-amine, and [Co(H2O)2trien][Cr(CN)6]·2H2O underwent deaquation-or deammonation-CN-bridging formation reaction upon heating. The general tendency was observed to be as follows: the more stable the structural configuration of the coordination sphere, the higher the activation energy. In the case of the complex containing hexacyanochromate(III) as an anion, the activation energy for the bridging formation reaction is especially high as a result of possible flipping in CN bridging groups.

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