The kinetics of formation of electron donor–acceptor complexes. A temperature-jump study

Abstract

. 68,278 (1990). The kinetics of the Electron Donor-Acceptor (EDA) complex between N,N,N',N1-tetramethyl-p-phenylenediamine and m-dinitrobenzene in acetonitrile has been studied by the temperature-jump technique. The magnitude of the rate constants of association and dissociation, although relatively large, is well below the diffusion control values. The calculated rates closely coincide with those obtained by chronoamperometry. An entropy control is suggested for this reaction. The results obtained in this work are useful to demonstrate that the concept about EDA complexes being formed by diffusion-controlled reactions should not be generalized.Key Chem. 68, 278 (1990). Utilisant la technique des sauts de temperature, on a 6tudi6 la cinetique du complexe accepteur-donneur Clectronique (ADE) f o m t par la N,N,Nf ,N'-tetramethyl-p-phenylknediamine et le m-dinitrobenzkne dans l'acetonitrile. L'amplitude de la constante de vitesse, mCme si elle est relativement importante, est beaucoup plus faible que les valeurs attendues sur la base d'un contr6le par diffusion. Les vitesses calcul6es coincident bien avec celles obtenues par chronoampCromCtrie. On suggkre que cette reaction est contr6lte par l'entropie. Les rksultats obtenus dans ce travail sont utiles pour dtmontrer que l'on ne devrait pas generaliser le concept selon lequel les complexes ADE se foment au cours de rtactions contr61Ces par la diffusion.Mots cle's : complexes accepteur-donneur electronique, m-dinitrobenzhe, N,N,N1,N'-tetramethyl-p-phCnyl2nediamine, saut de temperature, cinttique.[Traduit par la revue]

Kinetics of formation of charge transfer complexes of poly(vinyl pyridines) with iodine, 7,7′8,8′‐tetracyanoquinodimethane and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone by electronic spectroscopic studies

“…If the concentration of DA at equilibrium is &, then the net rate of the reaction at equilibrium is zero, that is, Equation (10) on rearranging, leads to Substituting equation (11) in equation (9) and, on simplification, we obtain dx kl ad(xex) (…”