ELECTRON TRANSFER RATESELECTRON TRANSFER RATES One important distinction between redox reactions of proteins and redox reactions of small transition-metal complexes is: e The magnitude of the electron donor-to-acceptor distance. e The relevant distance for small molecules, unlike redox proteins, is generally taken to be van der Waals contact. e Within the last ten years, it has been convincingly demonstrated that electrons can “tunnel” at significant rates across distances of 15 Aor more in protein interiors!!The factors that control the rates of biological redox reactions: “Box + Aros ——> “Aros + Aox Aox + Brea —> Aros + Box e Long-range electron transfers in biology are all of the outer-sphere typee The simplest electron transfer occurs in an outer-sphere reaction e This process involves geometric changes, changes in the interactions of the donor and acceptor with the surrounding solvent molecules.The Franck-Condon principleThe incorporation of the Franck-Condon restriction leads to the par- titioning®-© of an electron-transfer reaction into reactant (precursor complex) and product (successor complex) configurations. The steps in Equations (6.13) to (6.15) go from reactants to products: K is the equilibrium constant for the formation of the precursor complex [A,x, Beal, and k,; is the forward electron- transfer rate to produce the successor complex [A, 3 s 5 5 5 5 s z z 3 s a a a nuclear configuration nuclear configuration (A) (B) Figure 6.21 Potential energy diagrams: (A) self-exchange reaction; (B) cross reaction. Point § represents the activated complex. Ep and E> are the reactant and product surfaces, respectively.e The intersection of the reactant and product surfaces (point S) represents the transition state (or "activated complex")potential energy e Thus some degree of electronic interaction, or coupling, is required if the redox system is to pass from the precursor to the successor complex. nuclear coordinate a) @) (©)e If the degree of electronic interaction is sufficiently small, first-order perturbation theory can be used to obtain the energies of the new first-order surfaces, which do not cross. e The splitting at the intersection is equal to 2H»s , where Has is the electronic-coupling matrix element. e The magnitude of Hse determines the behavior of the reactants once the intersection region is reached. e Two cases can be distinguished. First, Has is very small; for these so-called "non-adiabatic" reactions, there is a high probability that the reactants will "jump" to the upper first- order potential energy surface, leading to very little product formation. e If the electronic interaction is sufficiently large, as it is for "adiabatic" reactions, the reactants will remain on the lower first-order potential energy surface upon passage through thei a E E, E E BO Ee po Be Ee Ee 2 5 z = 5 3 3 s 2 nuclear coordinate (A) (B) (c) Figure 6.22 Potential energy diagrams: (A) Hay = 0, « = 0 {no transfer); (B) Han small, K « 1 (nonadi- abatic transfer); (C) Has large, « = 1 (adiabatic transfer). The arrows indicate the relative prob ability of crossing to the product surface (Eg to Ep).Rudy Marcus Marcus received the Rudy Marcus in 2005 yess Nobel Prize in Chemistry July 21, 1923 (age 98) cya lm UR Ulloa Montreal, Quebec Rudolph Arthur MarcusGibbs Free Energy & Transition State Reactants Reaction Coordinate Reaction: HO + CH,8r > [HO—CH,-~Br]' > CH,OH + Bre Whereas, in TST the reaction partners become strongly coupled in the course of the reaction to form a structurally defined activated complex, in Marcus theory they are weakly coupled and retain their individualityThe Franck-Condon principleThe incorporation of the Franck-Condon restriction leads to the par- titioning®-© of an electron-transfer reaction into reactant (precursor complex) and product (successor complex) configurations. The steps in Equations (6.13) to (6.15) go from reactants to products: K is the equilibrium constant for the formation of the precursor complex [A,x, Beal, and k,; is the forward electron- transfer rate to produce the successor complex [A, 3 s 5 5 5 5 s z z 3 s a a a nuclear configuration nuclear configuration (A) (B) Figure 6.21 Potential energy diagrams: (A) self-exchange reaction; (B) cross reaction. Point § represents the activated complex. Ep and E> are the reactant and product surfaces, respectively.e The intersection of the reactant and product surfaces (point S) represents the transition state (or "activated complex")potential energy e Thus some degree of electronic interaction, or coupling, is required if the redox system is to pass from the precursor to the successor complex. nuclear coordinate a) @) (©)In classical transition-state theory, the expression for the rate constant of a bi- molecular reaction in solution is k = kv, exp (— AG*/RT ), (6.16) where v,, the nuclear frequency factor, is approximately 10'' M~! s~! for small molecules, and AG* is the Gibbs-free-energy difference between the activated complex and the precursor complex. This theoretical framework provides the starting point for classical electron-transfer theory. Usually the transmission coefficient « is initially assumed to be unity. Thus, the problem of calculating the rate constant involves the calculation of AG*, which Marcus partitioned into several parameters:Delta G* is the ee-energy difference between the activated complex and the precursor complex AG* = w" + (/4)(1 + AGP/A)?, AG” = AG? + w? — w’. Here w’ is the electrostatic work involved in bringing the reactants to the mean reactant separation distance in the activated complex, and w? is the analogous work term for dissociation of the products. These terms vanish in situations where one of the reactants (or products) is uncharged. AG® is the Gibbs-free- energy change when the two reactants and products are an infinite distance apart, and AG°' is the free energy of the reaction when the reactants are a distance r apart in the medium; AG? is the standard free energy of the reaction, obtainable from electrochemical measurements (the quantity — AG® is called the driving force of the reaction).AG* = w" + (M4)(L + AGA)’, AG°" = AG° + w? — w’. The reorganization energy A is a parameter that contains both inner-sphere (Aj) and outer-sphere (A) components; \ = A; + Ao. The inner-sphere reorga- nization energy is the free-energy change associated with changes in the bond lengths and angles of the reactants. The d, term can be evaluated within the simple harmonic-oscillator approximation: =) Bk; (Ax)?, (6.19) where &; values are normal-mode force constants, and the Ax; values are differ- ences in equilibrium bond lengths between the reduced and oxidized forms of a redox center.Marcus Theory of electron transfer The outer-sphere reorganization energy reflects changes in the polarization of solvent molecules during electron transfer: Ro = e*[(1/2ra) + (1/2rp) — (A/a) LU/Dop) — CDI; (6.20) d is the distance between centers in the activated complex, generally taken to be the sum of the reactant radii r, and rg; Dop is the optical dielectric constant of the medium (or, equivalently, the square of the refractive index); and D, is the static dielectric constant. This simple model for the effect of solvent reor- ganization assumes that the reactants are spherical, and that the solvent behaves as a dielectric continuum. (Sometimes the latter approximation is so rough that there is no correspondence between theory and experiment.)