Factors contributing to one-electron metalloradical activation of ethene and carbon monoxide illustrated by reactions of Co(II), Rh(II), and Ir(II) porphyrins

Metallo-porphyrin complexes of Co(II), Rh(II), and Ir(II) are used as prototype metal-centered radicals in examining the factors that contribute to obtaining one-electron activated ethene and CO substrate adducts [M(CH2CH2)] and [M(CO)] that subsequently react on to produce complexes with reduced substrate units including M–CH2CH2–M, M–(CH2)4–M, M–C(O)–M, M–C(O)–C(O)–M, and M–C(O)H. Cobalt(II) and rhodium(II) complexes of the form [(por)M(CH2CH2)] and [(por)M(CO)] occur as primarily metal-centered radicals and the iridium analogs are porphyrin anion radical complexes ((por)−IrIII(CH2CH2), (por)−IrIII(CO)). Relatively small (por)Co–C bond dissociation enthalpies preclude forming any reduced substrate species. Rhodium porphyrins produce a complete set of reduced and coupled ethene and CO complexes, but iridium porphyrins only give ethene reduction and coupling products (por)Ir–CH2CH2–Ir(por) and (por)Ir–(CH2)4–Ir(por). Thermodynamic criteria and analysis of substrate reactions are used to guide interpretations of the observed reactivity.

Graphical abstractThermodynamic criteria for one electron activation of ethene and carbon monoxide are described and used as a guide to interpret the patterns of reactivity for group nine (Co(II), Rh(II), and Ir(II)) porphyrin metal–metal bonded dimers and metalloradicals.Figure optionsDownload full-size imageDownload as PowerPoint slide