31G** and CCSD(T)/6-311++G**//MP2/6-31G** calculations have been used to investigate the H-abstraction reaction from CH 3 OCH 3 (DME) whereas MP2/6-31G**//MP2/6-31G** and PMP2/6-31G**//MP2/6-31G** levels have been used to model the H-abstraction reaction from (CH 3 ) 3 COCH 3 (MTBE) by OH. The methodology used has been proved to be adequate to reproduce the experimental geometrical parameters for the reactants and the C-H bond energies. The reaction rate constants for DME, calculated using the transition state theory reproduce the reported experimental results. The fact that H-abstraction is favored from the methoxy group of MTBE in comparison to the tert-butyl group has also been reproduced.y Electronic supplementary information (ESI) available: optimized structural parameters, energies, zero point energies and dipole moments for reactants, products, and transition states (Tables S1-8). See

The kinetics of the hydrogen abstraction from H 2 O 2 by•