AN ELECTROCHEMICAL STUDY OF SOLVENT-COMPLEX INTERACTIONS IN INOCYCLOHEXANE-N,N,N',N'-TETRAACETATOCHROMATE(III) AND ANE-N-HYDROXYETHYL-N,N',N'-TRIACETATOCHROMIUM(III)
M. Hecht et Wr. Fawcett, AN ELECTROCHEMICAL STUDY OF SOLVENT-COMPLEX INTERACTIONS IN INOCYCLOHEXANE-N,N,N',N'-TETRAACETATOCHROMATE(III) AND ANE-N-HYDROXYETHYL-N,N',N'-TRIACETATOCHROMIUM(III), Electrochimica acta, 41(9), 1996, pp. 1423-1433
The electroreduction of inocyclohexane-N,N,N',N'-tetraacetatochromate(
III) and ane-N-hydroxyethyl-N,N',N'-triacetatochromium(III) has been i
nvestigated in different solvents on a mercury electrode by convolutio
n potential sweep voltammetry. The dependence of the observed diffusio
n coefficients, standard potentials and double layer corrected electro
n transfer rates on solvent properties has been interpreted. It has be
en shown that the formal potentials for the reduction of both complexe
s are linear functions of the solvent acceptor numbers. The logarithm
of the corrected standard rate constant for the rans-1,2-diaminocycloh
exane-N,N,N',N'-tetraacetato complex depends on both the acceptor numb
er and the logarithm of the solvent's longitudinal relaxation time. On
the other hand in case of the ,2-diaminoethane-N-hydroxyethyl-N,N',N'
-triacetato complex, this quantity depends on the solvent's acceptor a
nd donor number. It is concluded that the ane-N-hydroxyethyl-N,N',N'-t
riacetatochromium(III) complex undergoes substitution of the coordinat
ed water molecule originally present as a ligand. However, for the ran
s-1,2-diaminocyclohexane-N,N,N',N'-tetraacetato chromium(III) complex
there is no indication of the incorporation of solvent molecules in th
e first coordination sphere as a ligand. Copyright (C) 1996 Elsevier S
cience Ltd.