Electrochemistry of Coordination Complexes

There have been two books that contain compilations of the electrochemistry of Os (572,573). There have also been reviews that cover the electrochemistry of certain classes of complexes with ligands such as porphyrins (142), dithiocarbamates (463), and macrocyclic complexes (39, 93). The purpose of this section is not to provide a comprehensive review of electrochemical studies over recent years, but rather to give some insight into the factors that affect the redox potentials and their use in obtaining information about 7r bonding and backbonding. Particular emphasis is placed on the similarities and differences between analogous Os and Ru complexes. 

Correlations have been made between gas-phase ionization potentials of free ions and the redox potentials of isostructural [MXe] complexes of the elements of the same row of the periodic table (476). Despite the observation of such correlations, caution must be taken, because they ignore both cr and tt ligand field effects. The latter are often more important in influencing the relative oxidizing or reducing strength of complexes. 

The developments in Os pentaammine chemistry described in this review have enabled an extensive library off 0 values to be obtained, spanning a range of 2 V (—200 kJ mol ) (Fig. 7). Table XIV compares the redox potentials of the Os(III/II) complexes with Ru(III/II) analogs versus the appropriate [M(NH3 6]3+/2+ couples. The data are presented in this manner in order to correct for solvent effects, which can be comparable with those induced by the v effects (574). The correction of 

6 The complexes of the cis and trans ligands have the same redox potentials. c The presence of this couple was not recognized in the original paper, but it is clearly present in Fig. 6 of Ref. 71 as a small response at potentials more negative than the main response that is due to the [Os(NH3)5(T)2-(aI erce)-CH2=CHPh) ,+,2+ couple. As can be seen from its position, its redox potential is consistent with an Tj2-arene structure. d 9-Anthracenecarbonitrile. 

Conversely, the stabilization of Os(IV) by 1 V per deprotonation in [Os(en)3]n+ (204,205) and the stabilization of higher oxidation states by deprotonation of aqua ligands (325) illustrate well the large effects brought about by it donation. 

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Electrochemistry provides a powerful tool for elucidating the pH-dependent redox mechanisms of coordination complexes. In principle, any electrochemically active chemical (or biological) system may exhibit pH-dependent reduction potentials, if the concomitant pH-dependent process occurs on the same timescale as electron transfer. While the pH-dependent process is ultimately chemical in nature (i.e., involves bond breaking and/or bond making), the phenomenon that perturbs the redox center and alters the reduction potential may be electronic, structural (e.g., a conformational change), or environmental (e.g., changes in solvation), and often will be some ill-defined combination of these factors. ... 

Other Coordination Complexes. Because carbonate and bicarbonate are commonly found under environmental conditions in water, and because carbonate complexes Pu readily in most oxidation states, Pu carbonato complexes have been studied extensively. The reduction potentials vs the standard hydrogen electrode of Pu(VI)/(V) shifts from 0.916 to 0.33 V and the Pu(IV)/(III) potential shifts from 1.48 to -0.50 V in 1 Tf carbonate. These shifts indicate strong carbonate complexation. Electrochemistry, reaction kinetics, and spectroscopy of plutonium carbonates in solution have been reviewed (113). The solubiUty of Pu(IV) in aqueous carbonate solutions has been measured, and the stabiUty constants of hydroxycarbonato complexes have been calculated (Fig. 6b) (90). 

Iron(II) alkyl anions fFe(Por)R (R = Me, t-Bu) do not insert CO directly, but do upon one-electron oxidation to Fe(Por)R to give the acyl species Fe(Por)C(0)R, which can in turn be reduced to the iron(II) acyl Fe(Por)C(0)R]. This process competes with homolysis of Fe(Por)R, and the resulting iron(II) porphyrin is stabilized by formation of the carbonyl complex Fe(Por)(CO). Benzyl and phenyl iron(III) complexes do not insert CO, with the former undergoing decomposition and the latter forming a six-coordinate adduct, [Fe(Por)(Ph)(CO) upon reduction to iron(ll). The failure of Fe(Por)Ph to insert CO was attributed to the stronger Fe—C bond in the aryl complexes. The electrochemistry of the iron(lll) acyl complexes Fe(Por)C(0)R was investigated as part of this study, and showed two reversible reductions (to Fe(ll) and Fe(l) acyl complexes, formally) and one irreversible oxidation process."" ... 

Coordination of NO to the divalent tetrasulfonated phthalocyanine complex [Co(TSPc)]4 results in a complex formally represented as [(NO )Coin(TSPc)]4 kf= 142M-1s-1, KA 3.0 x 105 M-1). When adsorbed to a glassy carbon electrode, [Co(TSPc)]4- catalyzes the oxidation and reduction of NO with catalytic currents detectable even at nanomolar concentrations. Electrochemistry of the same complex in surfactant films has also been studied.905 Bent nitrosyl complexes of the paramagnetic trivalent tropocoronand complex Co(NO)(TC) ((189), R = NO) have also been reported.849... 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

The first indication that such O-coordinated (phenoxyl)metal complexes are stable and amenable to investigation by spectroscopy was obtained when the electrochemistry of the colorless, diamagnetic complexes [Mm(LBu2)], [Mm(LBuMet)] (M = Ga, Sc) containing three coordinated phenolates in the cis-position relative to each other was investigated in acetonitrile solutions (142). A representative structure of [Scm(LBuMet)] is shown in Fig. 12. 

Table IV lists a series of octahedral (phenolato)chromium(III) precursor complexes that contain one or three oxidizable coordinated phenolato pendent arms (146, 154). These complexes display characteristic electrochemistry Each coordinated phenolato ligand can undergo a reversible one-electron oxidation. Thus complexes with one phenolato moiety exhibit in the C V one reversible electron-transfer process, whereas those having three display three closely spaced (AE1/2 250 mV) ligand-centered one-electron transfer processes, Eqs. (7) and (8).

Interface and colloid science has a very wide scope and depends on many branches of the physical sciences, including thermodynamics, kinetics, electrolyte and electrochemistry, and solid state chemistry. Throughout, this book explores one fundamental mechanism, the interaction of solutes with solid surfaces (adsorption and desorption). This interaction is characterized in terms of the chemical and physical properties of water, the solute, and the sorbent. Two basic processes in the reaction of solutes with natural surfaces are 1) the formation of coordinative bonds (surface complexation), and 2) hydrophobic adsorption, driven by the incompatibility of the nonpolar compounds with water (and not by the attraction of the compounds to the particulate surface). Both processes need to be understood to explain many processes in natural systems and to derive rate laws for geochemical processes. 

Recent work has resolved some of the issues that complicate direct electrochemistry of myoglobin, and, in fact, it has been demonstrated that Mb can interact effectively with a suitable electrode surface (103-113). This achievement has permitted the investigation of more complex aspects of Mb oxidation-reduction behavior (e.g., 106). In general, it appears that the primary difficulty in performing direct electrochemistry of myoglobin results from the change in coordination number that accompanies conversion of metMb (six-coordinate) to reduced (deoxy) Mb (five-coordinate) and the concomitant dissociation of the water molecule (or hydroxide at alkaline pH) that provides the distal ligand to the heme iron of metMb. 

ReCl3(PPh3)(benzil)] reacts with bipy and related ligands or terpy to form a number of rhe-nium(III) and rhenium(II) compounds which are useful precursors for the synthesis of lower-valent rhenium complexes. " Thus, reduction of [Re(bipy)3][PF6]2 with zinc amalgam results in the rhenium(I) compound [Re(bipy)3][PF6] in excellent yields. The corresponding terpyridyl bis-chelate [Re(terpy)2][PF6] has been prepared in a similar manner. " The electrochemistry of the products provides a convenient measure of the chemical reactivity associated with the redox processes. Thus, the one-electron oxidation of [Re(bipy)3]" is reversible at -0.33 V, whereas the Re"/Re" redox couple is irreversible and occurs at relatively low potentials (-1-0.61 V) which is consistent with the instability of [Re(bipy)3] + in solution. However, in the presence of a small coordinating molecule such as CNBu, oxidation to the rhenium(III) state is readily available by the formation of seven-coordinate complexes of the composition [Re(bipy)3(L)]. " ... 

A much more positive value of E° = —0.88 V is estimated in aqueous solution at pH >11 by using short-time pulse techniques [7, 8], The aqueous electrochemistry of Tc04 is complex. Under alkahne conditions, it is proposed that the protonation of Tc04 and/or the expansion of its coordination shell follows Eq. (1) and produces a more easily reduced Tc(VI) species, resulting in a multielectron transfer [8]. The subsequent reduction can... 

As regards other coordination compounds of silver, electrochemical synthesis of metallic (e.g. Ag and Cu) complexes of bidentate thiolates containing nitrogen as an additional donor atom has been described by Garcia-Vasquez etal. [390]. Also Marquez and Anacona [391] have prepared and electrochemically studied sil-ver(I) complex of heptaaza quinquedentate macrocyclic ligand. It has been shown that the reversible one-electron oxidation wave at -1-0.75 V (versus Ag AgBF4) corresponds to the formation of a ligand-radical cation. Other applications of coordination silver compounds in electrochemistry include, for example, a reference electrode for aprotic media based on Ag(I) complex with cryptand 222, proposed by Lewandowski etal. [392]. Potential of this electrode was less sensitive to the impurities and the solvent than the conventional Ag/Ag+ electrode. 

The current chapter focuses on the electrochemistry of the ionic forms of copper in solution, starting with the potentials of various copper species. This includes the effect of coordination geometry, donor atoms, and solvent upon the electrochemical potentials of copper redox couples, specifically Cu(II/I). This is followed by a discussion of the various types of coupled chemical reactions that may contribute to the observed Cu(II/I) electrochemical behavior and the characteristics that may be used to distinguish the presence of each of these mechanisms. The chapter concludes with brief discussions of the electrochemical properties of copper proteins, unidentate and binuclear complexes. 

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