Group nine metallo-porphyrins ((por)M) have been valuable in the evauation of M-X (X=C,H,O) bond dissociation energetics and in illustrating a wide range of metallo-radical and metallo-hydride small molecule reactions .Relatively weak (por)Co-CH3 (~38 kcalmol-1)and (por)Co-H (~50 kcalmol-1) result in applications of (por)CoII in the control of olefin radical polymerization through chain transfer catalysis and living radical polymerization. Relatively strong (por)Rh-CH3 (~57 kcalmol-1), average (por)Rh-H (61 kcalmol-1) and modest (por)Rh-OCH3 (46 kcalmol-1) are manifested in substrate reactions that establish the current scope of late transition metal radical and hydride small molecule transformations. Larger Ir-H (~67 kcalmol-1) compared to the Rh-H (61 kcalmol-1) makes X-H bond homolysis reactions more favorable for the iridium derivatives . Comparisons of group 9 bond dissociation energetics and substrate reactivity in organic and aqueous media will be presented .

Bond dissociation energetics and reactity of group 9 metallo-porphyrins: Controlled radical polymerization to hydrocarbon and water activation

245th National Meeting (2013)

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