inorganic electrochemistry - theory, practice and application 2003 - zanello

[...]... Complexes Containing Redox-active Ligands 1 Ferrocenes as Ligands in Metal Complexes 2 Fullerenes as Ligands in Metal Complexes 2.1 Intramolecular Electronic Communication in Metallo-bis(ful1erenes) 3 Dioxolenes (and Their Imino Analogues) and Dithiolenes as Ligands in Metal Complexes 4 Porphyrins (and Tetraazaporphyrins) as Ligands in Metal Complexes 5 Less Known Redox-active Ligands in Metal Complexes... Introduction 2 Electrochemistry of Cytochromes 3 Electrochemistry of Iron-Sulfur Proteins 4 Electrochemistry of Blue Copper Proteins References Chapter 13 Linear Correlations Between the Redox Potential and Other Chemical and Physico-chemical Parameters 1 Redox Potential and Electronic Effects of the Ligands 2 Redox Potential and Solvent Effects 3 Redox Potential and Temperature References 505 506 507 508... Blues 2 Chloride-Bridged Triruthenium Complexes 3 Oligo-2-Pyridylamides as Bridging Ligands in Polynuclear Linear Complexes 3.1 Trinuclear Complexes 3.2 Tetranuclear Complexes 3.3 Pentanuclear Complexes 3.4 Higher Nuclearity Complexes 4 Isocyanides and Nitrile Ligands in Polynuclear Linear Complexes References Chapter 12 The ‘Direct’ Electrochemistry of Redox-active Proteins 1 Introduction 2 Electrochemistry. .. interactions between reagents and electrode, in the case of reactions in a heterogenous phase; formation of short- or long-lived intermediates due to variations in electronic configurations, to the eventual substitution of ligands, etc Commonly, oxidation-reduction reactions in a homogenous phase are classified as: outer-sphere reactions; inner-sphere reactions In the inner-sphere reactions, the process... reaction rate, v (in mol s-I) Figure 4 A schematic way to set up the reduction reaction: Ox electrode + ne- -+ Red, at an 15 Fundamentals of Electrode Reactions Since we are considering heterogeneous processes, the rate of which is commonly proportional to the area of the electrode, one can normalize with respect to the electrode area, A , so that: i - 1 dM - v(mo1 s-l n F - A A dt m-2> This expression... chemical and biological mechanisms and a number of such examples will be illustrated in the text Perhaps in no other field of chemical reactivity has one looked for and found so many relationships between theory and experimental measurements Two disciplines cover the majority of the theoretical and practical aspects of the mechanisms through which electron transfers proceed: electrochemistry and photochemistry... " , of the couples S j S - and S'jS, respectively + - + - 16 Chapter 1 POSSIBLE PERTURBATIONS OF THE ELECTRODE POTENTIAL ELECTRODE REDUCTION REDOX-ACTNE SPECIES S I eleckons of me species s % I OXIDATION HOMO Fermi Q level + - Fermi level nrl (b) Figure 5 The potential of an electrode can be perturbed in order to trigger: ( a ) reduction processes; ( b ) oxidation processes - Let us consider the case... example, the reduction of acetic acid proceeds through the two microscopic stages: CH,COOH H+ 0 + e- CH3COO- - 1 ;H2 + H+ (PRECEDING CHEMICAL REACTION) (ELECTRON TRANSFER) adsorption In the sequence of reactions (2 )-( 3 )-( 4) it was assumed that electron exchange takes place without the interaction of the species Ox and Red with the electrode surface However, it is possible that the exchange of electrons does... Metal Clusters 1 Metal-Sulfur Clusters 1.1 M3S, ( ~ 1 = 2 ,4) 1.2 M4Sn (n = 3-6 ) 1.3 M6S, (n= 6, 8, 9) 1.4 M9S9 2 Metal-Carbonyl Clusters 2.1 M3(C0)12,LM3(CO)II] 2- = Fe, Ru, 0 s ) (M 2.2 [Fe4(CO)13 ]-, M4(C0)12 (M = Co, Rh, Ir) 2.3 [M-j(CO)lSln- (M = OS,~ 1 =2; M = Rh, n = 1) 2.4 [M6(C0)15] 2-( M = Co, Rh, Ir), 409 346 348 363 371 374 392 397 399 402 404 407 409 409 414 419 42 1 422 422 42 5 426 xii Contents... ++ 5NHi - The fact that from a chloro-cobalt complex a chloro-chromium complex is formed, suggests that the reaction must proceed through an intermediate state that enables the transfer of a chlorine atom from cobalt to chromium The proposed mechanism for this reaction is: [Cr"(H,0)6]2++[ C O " ' ( N H ~ ) ~ C ~ ] ~ + {[(H20)5Cr11 C 1- Co1"(NH3),]4++H;0 electron transfer I i {[(H20)5Cr"1 - C 1- C O " . w0 h0" alt="" Inorganic Electrochemistry Theory, Practice and Application