Scheme 3. (a) Radical trapping experiment. (b) H/D-Exchange study. (c) Headspace GC analysis after catalysis (left side) and measurement of gas evolution during catalysis (right side). (d) Cyclic voltammetry studies. (e) Relative Gibbs free energies (ΔG338.15) are given in kcal mol−1 for the ruthenium-catalyzed ortho-C–H phosphorylation reductive elimination step at the PBE0-D4/def2-TZVPP-SMD(HFIP)//PBE0-D3BJ/def2-SVP level of theory. In the computed transition state structure, non-relevant hydrogens were omitted for clarity. (f) Plausible reaction mechanism for the ruthenaelectro-catalyzed ortho-C–H phosphorylation.27.
