The application of high pressure kinetic techniques have contributed significantly towards the elucidation of inorganic reaction mechanisms.1 In these studies the effect of pressure on the chemical process enables the construction of a volume profile, on which basis mechanistic information can be obtained. The investigated reactions include ligand substitution, activation of small molecules and electron transfer processes.1 A general overview of the employed technology and specific examples from our most recent investigations will be presented. We have studied the interaction of NO with metmyoglobin2 and reduced cobalamin.3 In these systems a combination of stopped-flow and flash-photolysis kinetic techniques were employed to measure the "on" and "off" rate constants, as well as their temperature and pressure dependences, from which all activation parameters ((H#, (S# and (V#) could be estimated, and energy and volume profiles could be constructed. The latter reveal detailed information on the intimate nature of the binding process. The results allow a direct comparison with related solvent exchange processes.4
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1. R. van Eldik, C. Dücker-Benfer, F. Thaler, Adv. Inorg. Chem., 49, 1 (2000); R. van Eldik, C.D. Hubbard, Chemie in unserer Zeit, 34, 240 (2000); R. van Eldik, D. Meyerstein, Acc. Chem. Res., 33, 207 (2000).
2. L.E. Laverman, A. Wanat, J. Oszajca, G. Stochel, P.C. Ford, R. van Eldik, J. Am. Chem. Soc., 123, 285 (2001).
3. M. Wolak, A. Zahl, T. Schneppensieper, G. Stochel, R. van Eldik, J. Am. Chem. Soc., submitted for publication.
4. T. Schneppensieper, A. Zahl, R. van Eldik, Angew. Chemie, in press.

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