The peroxides from methylrhenium trioxide (MTO) and hydrogen peroxide, CH 3ReO 2(η 2-O 2), A, and CH 3Re(O)(η 2-O 2) 2(H 2O), B, have been fully characterized in both organic and aqueous media by spectroscopic means (NMR and UV−vis). In aqueous solution, the equilibrium constants for their formation are K 1 = 16.1 ± 0.2 L mol - 1 and K 2 = 132 ± 2 L mol - 1 at pH 0, μ = 2.0 M, and 25 °C. In the presence of hydrogen peroxide the catalyst decomposes to methanol and perrhenate ions with a rate that is dependent on [H 2O 2] and [H 3O +]. 
The complex peroxide and pH dependences could be explained by one of two possible pathways: attack of either hydroxide on A or HO 2 - on MTO.
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The respective second-order rate constants for these reactions which were deduced from comprehensive kinetic treatments are k A = (6.2 ± 0.3) × 10 9 and k MTO = (4.1 ± 0.2) × 10 8 L mol - 1 s - 1 at μ = 0.01 M and 25 °C. The plot of log k ψ versus pH for the decomposition reaction is linear with a unit slope in the pH range 1.77−6.50. The diperoxide B decomposes much more slowly to yield O 2 and CH 3ReO 3.
This is a minor pathway, however, amounting to.
The serious study of the reaction mechanisms of transition metal com plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Higgision, E.1. Wilkins.A larger community of research scientists then entered the field, many of them stu dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub stitution and oxidation-reduction reactions.
Mechanistic inorganic chemistry thus took on a shape of its own. This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading.