Compounds [Cp*(2)M(2)O(5)] (M = Mo, 1; W, 2) are efficient pre-catalysts for cyclooctene (COE) epoxidation by aqueous H(2)O(2) in acetonitrile/toluene. The reaction is quantitative, selective and takes place approximately 50 times faster for the W system (k(obs) = 4.32(9)x10(-4) s(-1) at 55 degrees C and 3x10(-3) M concentration for the dinuclear complex, vs. 1.06(7)x10(-5) s(-1) for the Mo system). The rate law is first order in catalyst and COE substrate (k = 0.138(7) M(-1) s(-1) for the W system at 55 degrees C), whereas increasing the concentration of H(2)O(2) slows down the reaction because of an inhibiting effect of the greater amount of water. The activation parameters for the more active W systems (DeltaH(double dagger) = 10.2(6) kcal mol(-1); DeltaS(double dagger) = -32(2) cal mol(-1) K(-1)) were obtained from an Eyring study in the 25-55 degrees C temperature range. The H(2)O(2)urea adduct was less efficient as an oxidant than the aqueous H(2)O(2) solution. Replacement of toluene with diethyl ether did not significantly affect the catalyst efficiency, whereas replacement with THF slowed down the process. The epoxidation of ethylene as a model olefin, catalysed by the [Cp*MO(2)Cl] systems (M = W, Mo) in the presence of H(2)O(2) as oxidant and acetonitrile as solvent, has been investigated by DFT calculations with the use of the conductor-like polarisable continuum model (CPCM). For both metal systems, the rate-limiting step is the transfer of the hydroperoxido O(alpha) atom to the olefin, in accordance with the first-order dependence on the substrate and the zero-order dependence on H(2)O(2) found experimentally in the catalytic data. The activation barrier corresponding to the rate-limiting step is 4 kcal lower for the W complex than for the corresponding Mo analogue (32.3 vs. 28.3 kcal mol(-1)). This result reproduces well the higher catalytic activity of the W species. The different catalytic behaviour between the two systems is rationalised by a natural bond orbital (NBO) study and natural population analyses (NPA). Compared to Mo, the W(VI) centre withdraws more electron density from the sigma bonding [O-O] orbital and favours, as a consequence, the nucleophilic attack of the external olefin on the sigma*[O-O] orbital.