Based on homolytic Pd(II)-C cleavage from the ground state Tshaped complexes summarized in Eq 2, the bond dissociation free energy and enthalpy were calculated to be BDFE (BDE) = 34.3 (47.0) and 46.5 (33.5) kcal/mol for T-shaped complexes 1a and 1b, respectively (DLPNO-CCSD(T)/def2-TZVPP//B3LYP-D3/6-311G++(d,p)/LANL2DZ(Pd); see ESI for full details). These data are consistent with experimental observations that homolysis does not occur from the ground state under thermal conditions alone. Isodesmic reactions (Eq 3 and 4) were also used to estimate the free energy change in the Pd(II)-CH3 bond upon excitation from the ground to triplet state (see ESI, page S139 for full details). These calculations used the experimentally determined BDFE for [Pd(II)-CH3] + (59 kcal/mol) based on ion beam reactive scattering. Experimental BDFEs of more closely related Pd(II)-CH3 complexes were not found, but relative energy changes benchmarked against this gas phase species are