Derivatographic Studies on Transition Metal Complexes. XX. Thermal Electron Transfer Reactions of Cobalt(III) Complexes Containing Phenylbiguanide in the Solid Phase

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Abstract
The following six cobalt(III) complexes containing phenylbiguanide were prepared and the thermal reactions were followed both isothermally and non-isothermally (derivatographically) in the solid phase: trans-[Co(A)2(phbgH)2]X3·n2O, where A denotes volatile ligands such as NH3, CH3NH2 or C5H5N; phbgH denotes 1-phenylbiguanide, X chloride or bromide ion; and n is 2 or 3. From the electronic, IR and far-IR spectra and magnetic susceptibilities of these complexes before and after heating, the products obtained by evolving volatile ligands were found to be uniform bivalent cobalt complexes without rupture of the bonds of phbgH to cobalt in spite of the reduction of central cobalt(III) ion, except for the complexes containing ammonia. The reaction seems to be caused by the electron transfer from the coordinated phbgH to cobalt, not from the outer-sphere anions.

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