Free-radical substitution reactions. Bimolecular homolytic substitutions (SH2 reactions) at saturated multivalent atoms (Ingold, K. U.)

Quantum Chemical Studies of Radical Cation Rearrangement, Radical Carbonylation, and Homolytic Substitution Reactions

Solvent-free Substitution Reactions of Solid Phosphines

Reactions of (η-RC5H4)Fe(CO)2I (R = H, Me) complexes with phosphine ligands PR′3 (R′ = Ph, m-Tol, p-C6H4OMe, p-C6H4Cl, p-C6H4F) have been performed under solvent-free conditions in the melt phase and generally yielded the ionic products [(η5-RC5H4)Fe(CO)2PR′3]I rather than the CO substituted products (η5-RC5H4)Fe(CO)(PR′3)I. The complexes have been characterised by IR, NMR and MS techniques. By...

Equilibration in Reversible Bimolecular Reactions

Fast reversible pseudo-unimolecular reactions do not approach equilibrium in the simple exponential fashion predicted by chemical rate equations. Many-body effects in bimolecular reactions have been revealed in an extensive series of Brownian simulations, showing up to three distinct phases in the approach to equilibrium. Recent theoretical developments are compared with the simulation as well ...

Physiological aspects of free-radical reactions.

Enzymes which catalyze the formation of free radicals in vitro will catalyze similar reactions in vivo. We believe that the formation of some kinds of free radicals has definite physiological meanings in metabolism. In this sense, the enzymes forming such free radicals are concluded to be in evolutionally advanced states. Elaborated structure and function of enzymes such as horseradish peroxida...

Kinetic Studies of Some Free Radical Reactions

Kinetic and mechanistic studies on some characteristic freeradica1 reactions are reviewed briefly. The unimolecular rearrangements: RCMe2CH ÷ Me2CCH2R, fall into two classes. Class 1: R = R'C(O)O for which the 1,2—migration occurs via a 5—eenter cyclic transition state with considerable charge separation, [R'C02 Me2CCH2]*. Class 2: R = H2C=CH, Me3CC=0, C6H5, Me3CCsC, and CsN, for which migratio...