Metalloradical activation of methane

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

“…2 [CH 4 ]) and large kinetic isotope effects ðk H =k D > 8Þ derived from kinetic studies of the reactions in Fig. 58 (166,167), are consistent with the proposed concerted four-centered pathway with a near linear transition state in Fig. 59(a).…”

“…58). Introducing further steric requirements beyond those of TMP (as in the porphyrins TTEPP or TTiPP) is expected to result in weaker RhÀ ÀC bonds, thereby disfavoring the CÀ ÀH activation process (167).…”

Germanium(iii) corrole complex: reactivity and mechanistic studies of visible-light promoted N–H bond activations

“…Combining the aforementioned observations, the N-H bond activation by 1 most likely proceeds via a termolecular transition state (Scheme 3) similar to that proposed for methane activation by rhodium porphyrin complexes 24 and the activation of NH 3 by a palladium pincer dimer.…”

Selective CC Coupling of Ir–Ethene and Ir–Carbenoid Radicals

“…One-electron oxidative addition of organic halides to the metal is a key step in Ru-catalyzed atom-transfer radical polymerization [3] and in Ru-, [4] and Rh/Ir-catalyzed [4d] atom-transfer radical addition of polyhalogenated compounds to olefins. In addition, Rh IIporphyrin complexes are capable of homolytic cleavage of inert C À H bonds of methane [5] or methanol [6] and cleave the C À C bonds of ketones, [7] nitriles, [8] and the 2,2,6,6-tetramethylA C H T U N G T R E N N U N G piperidine-N-oxide radical (TEMPO).…”