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Understanding Reaction Dynamics in Coordination Chemistry—Application of High Pressure Techniques
Author(s) -
van Eldik Rudi
Publication year - 1986
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198606731
Subject(s) - chemistry , kinetic energy , chemical reaction , mechanism (biology) , chemical kinetics , reaction mechanism , reaction rate , biochemical engineering , computational chemistry , kinetics , transition state theory , chemical physics , statistical physics , thermodynamics , catalysis , reaction rate constant , organic chemistry , physics , quantum mechanics , engineering
In order to understand the dynamics of chemical reactions in general, detailed information on electronic, structural and kinetic properties is required. The key questions on how chemical reactions actually occur can in many cases only be answered in terms of information obtained from kinetic studies. In conventional kinetic studies of chemical reactions in solution, the variables usually selected include concentration, acidity, solvent, and temperature. In recent years, pressure has become an additional selected variable in such studies. It enables the measurement of the volume of activation and the construction of reaction volume profiles and thus assists in the elucidation of the underlying mechanism; it also completes the comprehension of reaction kinetics by adding another kinetic parameter that the suggested reaction mechanism must account for. Furthermore, the volume of activation is the only transition state property that can be correlated with the corresponding ground state property in an experimentally simple manner. In this paper, the insights so gained in our understanding of the dynamics of reactions involving coordination complexes will be presented. Such reactions are of fundamental interest to chemists since they often form the basis of catalytic, biological, environmental and energy related processes. Any additional information that will add to the understanding of the reaction dynamics is therefore of exceptional importance.