(A) Normalized TRIR kinetic traces showing the decay of CpRh(CO)(alkane) and the formation of CpRh(CO)(alkyl)H obtained following irradiation of a solution in either scCH4 [(i), (ii)], C5H12 [(iii), (iv)], or C10H22 [(v), (vi)]. (B) A plot of the lifetimes for the C─H activation reaction for the linear alkanes as a function of C the number of carbon atoms for (vii) CpRh(CO)(alkane) and (viii) Cp*Rh(CO)(alkane).