The sulfur-bridged dimeric dithiolato rhenium(V) chelate ( D), derived from 2-mercaptothiophenol, was monomerized to give ( M− L) in benzene upon reaction with various neutral and anionic monodentate ligands ( L) such as pyridine and its substituted derivatives, triarylphosphines, dimethyl sulfoxide, 4-picoline- N-oxide, and halide ions. The kinetic observations can readily be interpreted for all ligands by a unified mechanism in which the initial fast formation of a 1:1 ( DL) and 1:2 ( DL 2) adduct is followed by the slow monomerization of each species so formed. The use of different ligands gave insight into different steps of the same multistep mechanism.
This Perspective presents a personal overview of the current status of the theory of chemical kinetics and mechanisms for complex processes. We attempt to assess the status of the field for reactions in the gas phase, at gas–solid interfaces, in liquid solutions, in enzymes, and for protein folding. Some unifying concepts such as potential energy surfaces, free energy, master equations,. Chemical Kinetics and Reaction Mechanisms by James Espenson and a great selection of related books, art and collectibles available now at AbeBooks.com.
The kinetics of ligand exchange between free L and the monomeric complexes was also studied; an associative pathway has been proposed to interpret the results. The crystal structures of two new monomeric ML complexes (with L = 4-acetylpyridine and 1,3-diethylthiourea) are reported.
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This Perspective presents a personal overview of the current status of the theory of chemical kinetics and mechanisms for complex processes. We attempt to assess the status of the field for reactions in the gas phase, at gas–solid interfaces, in liquid solutions, in enzymes, and for protein folding.
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Some unifying concepts such as potential energy surfaces, free energy, master equations, and reaction coordinates occur in more than one area. We hope this Perspective will be useful for highlighting recent advances and for identifying important areas for future research.