A Computational Study of the Olefin Epoxidation Mechanism Catalyzed by Cyclopentadienyloxidomolybdenum(VI) Complexes

A DFT analysis of the epoxidation of C2H4 by H2O2 and MeOOH (as models of tert-butylhydroperoxide, TBHP) catalyzed by [CP*MoO2Cl] (1) in CHCl3 and by [Cp*MoO2(H2O)](+) in water is presented (Cp*=pentamethyl-cyclopentadienyl). The calculations were performed both in the gas phase and in solution with the use of the conductor-like polarizable continuum model (CPCM). A low-energy pathway has been identified, which starts with the activation of ROOH (R=H or Me) to form a hydro/alkylperoxido derivative, [Cp*MoO(OH)(OOR)Cl] or [Cp*MoO(OH)(OOR)](+) with barriers of 24.9 (26.5) and 28.7 (29.2) kcal mol(-1) for H2O2 (MeOOH), respectively, in solution. The latter barrier, however, is reduced to only 1,0 (1.6) kcal mol(-1) when one additional water molecule is explicitly included in the calculations. The hydro/alkylperoxido ligand in these intermediates is eta(2)-coordinated, with a significant interaction between the Mo center and the O-beta atom. The subsequent step is a nucleophilic attack of the ethylene molecule on the activated O-alpha atom, requiring 13.9 (17.8) and 16.1 (17.7) kcal mol(-1) in solution, respectively. The corresponding transformation, catalyzed by the peroxido complex [Cp*MoO(O-2)Cl] in CHCl3, requires higher barriers for both steps (ROOH activation: 34.3 (35.2) kcal mol(-1); O atom transfer: 28.5 (30.3) kcal mol(-1)), which is attributed to both greater steric crowding and to the greater electron density on the metal atom.