Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl2(C2H4), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C-H activation of benzene. The Os(PyBox)Cl2(C 2H4) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson-Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG‡ = 32.0 kcal/mol) is more reactive for benzene C-H activation than Ru/PyBox in basic conditions (ΔG‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.
All Science Journal Classification (ASJC) codes
- Process Chemistry and Technology
- Physical and Theoretical Chemistry