Optical activity high-pressure experiments

An UV-visible-near-IR high-pressure optical unit [30] equipped with pillbox cells [31] was used for the kinetic experiments. Here the observed small negative activation volume does not necessarily indicate an associatively activated reaction pathway. Indeed, the AVs determined is a composite one, as it includes the activation volume of the rate-determining step and the unknown reaction volume. Attempts to perform the reverse reaction, the synthesis of CH3Re03 from CH4 (200 MPa) and Re04, failed, so the hydrolysis of CH3Re03 seems to be irreversible. 

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