ABSTRACT
The kinetics and mechanisms of the redox reactions of oxidant, -adipato-di(N,N/-bis(salicylidene)ethylenediaminatoiron(III),[(Fe-salen)2adi],hereafter denoted as Fe2adi, with the thiols L-cysteine (LSH), thiourea (USH), thioglycolicacid(GSH),2–mercaptobenzothiazole (BTSH) and benzylmercaptan (BSH) have been studied spectrophotometrically at 495 nm in aqueous perchloric acid, I=0.01mol dm-3 (NaClO4) and at 29 1oC. The stoichiometry of 1:1 was obtained for Fe2adi – LSH, Fe2adi – GSH and Fe2adi –BTSH systems while 1:2 was obtained for Fe2adi – USH and Fe2adi–BSH systems. Under pseudo – first order conditions of a large excess of the reductants, pseudo–first order rate constants increased with increase in concentrations of the thiols (LSH, USH, GSH and BTSH), but decrease in pseudo – first order rate constant was observed as the concentration of BSH increased. The second order rate constants k2 were fairly same for all the five systems with values. 0.009 0.003 dm3 mol-1 s-1, 0.063 0.01dm3 mol-1 s-1, 0.038 0.005 dm3 mol-1 s-1, 0.011 0.001 dm3 mol-1 s-1. and. 0.0015 0.0035 dm3 mol-1 s-1 for LSH, USH, GSH, BTSH and BSH respectively. The rates of reaction were directly dependent on acid concentrations for the five systems. The overall rate equation for the reactions can be given as [Fe2adi] [reductant] [ ] for Fe2adi–LSH, Fe2adi – GSH, and Fe2adi – BTSH systems where a and b are the intercept and slope respectively, [Fe2adi] [USH]2 for Fe2adi–USH, while the rate equation, was for Fe2adi –BSH system is [Fe2adi] [BSH] [ ]2. The values of a and b obtained for the reaction of Fe2adi with the thiols are given as LSH (a = 0.3 x 10-4 dm3mol-1 s-1 and b = 1.23 x 10-3 dm6 mol-2 s-1), USH (a=6.2×10-4 dm3mol-1s-1 and b = 6.4 x10-3 dm6mol-2s-1), GSH (a = 1.9 x 10-4 dm3mol-1s-1 and b = 8.18 x 10-2 dm6mol-2 s-1), BTSH (a = 0.51 x 10-5 dm3mol-1s-1 and b = 2.0 x 10-3 dm6mol-2s-1), BSH (b =8.0 x 10-3 dm6mol-2 s-1). The rates of reactions was observed to decrease with the increase in ionic strength of the medium for the five systems under study. Addition of magnesium and acetate ions in small amount did not affect the rates of reactions for the redox reactions of Fe2adi with LSH, USH, GSH and BTSH, but decrease in rates of reaction was observed for that of BSH. The rates of reaction were not affected by the decrease in dielectric constant D for the reaction of Fe2adi with LSH, GSH and BTSH but it was enhanced for USH and BSH under the same conditions. Furthermore, the activation parameters, H# and S# were also determined for the five systems; the values being 89.99kJmol-1 and -30195Jk-1 mol-1 for Fe2adi-LSH system, 20.68kJmol-1 and -197.60Jk-1mol-1 for Fe2adi-USH system, 27.38kJmol-1 and-303.48JK-1 mol-1 for Fe2adi-BTSH system and 12.83kJmol-1 and -313.82JK-1mol-1 for Fe2adi-BSH system. Michaelis-Menten plot of 1/kobs versus 1/[reductants] were linear with intercepts for the redox reactions of Fe2adi with LSH, GSH, BTSH, USH and BSH. On the basis of the results obtained above, the reactions have been proposed to follow the inner-sphere mechanism.
CHAPTER ONE
- INTRODUCTION
The electron transfer reactions of binuclear iron (III) complexes have attracted a lot of interest in recent time due to their application as models for the investigation of the physiological role played by iron in biochemical processes 2, such as hemerythrin 2,3,4.6 and ferric porphyrin7,27,28 47. Previously, the dynamics of electron transfer reactions of dinuclear oxo bindged iron(III) complexes of the form [Fe2O]4+ with ascorbic acid 4, mercapto acetic acid5 and mercaptoethylamine 6 have been investigated. Most of these reactions followed outer sphere electron transfer route with intervening ion-pair complexes and free radicals..
The behaviour of transition metal ions with respect to their electron transfer and the roles played by bridging ligands in the course of redox reaction formed the bed rock of this study. 37,39 The main advantage of this research is that the results provide additional insight into the complexities attending reactions of bridged iron(III) complexes and the extent of influence of the bridging ligand on the rate of electron transfer. It is therefore hoped that this research will enhance the knowledge of the kinetics and mechanisms of electron transfer reactions of binuclear iron (III) complexes and other transition metal complexes with these set of thiols.
1.2 Methods of Monitoring Reaction Rates
The first step in kinetic analysis of a given reaction is to ascertain the stoichiometry of the reaction and to identify any side reaction. The fundamental data of chemical kinetics are the concentrations of the reactants and products at different times after a reaction has been initiated.1 The rates of most chemical reactions are sensitive to the temperature aid. In conventional experiments, the temperature of the reaction mixture must be held constant throughout the course of the reaction.
The method employed in monitoring the rate of a reaction depends on the concentration of the species involved and on how fast the concentrations change. Reactions may take seconds, minutes or hours before they can reach equilibrium. The techniques used to monitor the change in concentration are as follows:
1.2.1 Conventional Method (Slow Technique)
Conventional methods involve the measurement of the concentration or any physical property of one or more of the reactants or products as a function of time. For instance, in some reactions absorbance of any of the reactants or products could be measured and related directly to the concentration.
In kinetic analysis, the composition of the system is examined while the reaction is in progress by either withdrawing a small sample or the bulk and the reactants are mixed as they flow together in a reaction container. At different level in the observation tube, the mixtures are examined at different time of mixing and by doing so, the rate of the reaction is obtained
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