Photo-and Radiation-Induced Reactions

The effect of pressure on photochemical and photo-induced reactions has been investigated in detail for many systems, and a number of reviews have appeared on this subject recently [82-84]. This topic is treated in more detail in Chapter 6, and readers are referred to that chapter for more information. 

Pulse-radiolysis is a well-established technique for investigating the interaction of free radicals with metal complexes. For instance, with this technique metal 

A typical example of a volume profile for the formation and cleavage of a C0-CH3 bond is reported in Fig. 1.28 for the reaction shown in Eq. (1.13) [86]. 

1 Effect of Pressure on Inorganic Reactions Introduction and Mechanistic Applications 

The volume profile indicates an increase in partial molar volume in proceeding to the transition state, which is interpreted in terms of an substitution controlled binding of the methyl radical to the Co(ll) complex. The large volume collapse that occurs subsequent to the formation of the transition state is ascribed to metal-carbon bond formation which is accompanied by oxidation of Co(II) to Co(III) and accompanied by a large volume contraction [86]. 

---