ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of electron transfer from hexacyanoferrate(II) to tris(dimethylglyoximato)-nickelate(IV), Ni(dmg)32-, to produce Fe(CN)63- and Ni(dmgH)2, follows a pseudo-first-order disappearance in the Ni(IV). The pseudo-first-order rate constants kobs are linearly dependent on [Fe(CN)64-]0 in a fiftyfold range of 2 × 10-4-1 × 10-2M, and the average values of kobs/[Fe(CN)64-]0 range from 194M-1·s-1 at pH = 5.20 to 0.2M-1·s-1 at pH = 9.07 in aqueous medium at 35°C and μ = 0.57M. Results are interpreted in terms of a probable mechanism involving rate-determining outer sphere one-electron transfer steps from the reductant and one-protonated reductant species to the unprotonated and one-protonated Ni(IV) species present in solution. The more electrophilic one-protonated reductant species apparently reacts several orders of magnitude faster than the unprotonated one.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550150811
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