Oxidation-reduction reactions between cobalt(II) and -(III) chelate and iron(III) and -(II) cyanide complexes. Outer- vs. inner-sphere mechanisms

Kinetics and Mechanisms of the Reaction of Aluminium(III) with Polyaminocarboxylic Acids

“…The value of the outer-sphere association constant calculated for a +3/-2 interaction using the Eigen-Fuoss equation [22,23] is 17 mol -1 dm 3 which is considerably less than the value experimentally determined. However, in a number of instances where the possibility of hydrogen bonding was present, values of Kos Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 5/31/15 7:33 PM significantly larger than those calculated on the basis of charge has been found [24][25][26]. Indeed, Martinez et al [26] have reported values of greater than 100 for reaction of [Fe(CN)6] 4~ with uninegative cobalt(III) complexes containing phosphate ligands and hydrogen bonding was postulated to play a significant role.…”

Kinetics of the Electron‐Transfer Reactions between (Ethylenediaminetetraacetato) Cobaltate (III) and (4‐Aminopyridine)Pentacyanoferrate (II) Complexes

“…Substituting these work terms into Eq. 6 However, in changing from Cofedta}? to Co(edta)', the complex undergoes a spin change from a high-spin state (Co(lI» to a low-spin state (Co(IlI» which cannot becompleted in one step.…”

“…and the other bythe outer-sphere reaction with Fe(CN)sL3and Co(edta): as the final products. Although the electrontransfer reactions of the Fe(CN)sL2--Co(edta)2-system have been established, little effort has been devoted to the reaction between Fe(CN)sL3-and Cofedta): 4,6 or forward reaction ofEq. 1. kc,OI Fe(CN)sU + Co(edta)-;==l: Fe(CN)sU + Cofedta)" (1) kc,OI One reason for the lack of interest may be the large reduction potentials of Fe(CN)sLU3-couples, which make it difficult to fmd suitable experimental conditions to favour the forward reaction of Eq.…”

Picosecond Spectroscopy: Methods and Recent Applications

“…An example in the area of organometallic chemistry is the picosecond absorption study by Reagor et al (27), which measured the ki netics of intramolecular electron transfer in binuclear, bridged (NC) 5 Fe n -CN-Co nl (chelate) com plexes. The reduction of hexacyanoferrate(III) ion (Fe(CN)|-) by ethylenediaminetetraacetatocobaltate(II) (CoEDTA 2-) had been shown previ ously to undergo reaction by the mechanism depicted in Scheme I (28,29). Fe n -CN-Co m bridged species are formed when two com plexes are prepared by mixing either N-hydroxyethylethylenediaminetriacetatocobaltate(II) (Co»HEDTA) or N-benzylethylenediaminetriacetatocobaltate(II) (Co n NBETA) with Fe(CN)6~.…”