Reactivity Trends in Oxidative-Addition Reactions

FIGURE 6.8 The state correlations in the VBSCDs of oxidative—additions of (a) a carbenoid reagent into a C—H bond, and (b) a transition metal complex into a C—X bond. 

These oxidative—addition reactions have been treated extensively by Su et al. (29-31), using the VBSCD model. In all cases, a good correlation was obtained between the computed barriers of the reaction and the respective AEst quantities (which enter into the expression of G), including the relative reactivity of carbenoids, and of PtL2 versus PdL2 (29-31). Another treatment led to the same reactivity patterns for C—F bond activation reactions by Rh(PR3)2X and Ir(PR3)2X d8 complexes, which are isolobal to carbenoids (30). A similar extended correlation was found recently for C—Cl activation by d10-PdL2 (32), and is dealt with in Exercise 6.9. 

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