The reactants, ion-dipole complexes, transition states, and products for the proton transfer reactions HBCOH+ + OCXH → HBCO + +HOCXH optimized at the SCF/4-31G* level of theory for B, X = F, Cl, H, CH3, CH2Cl, CHCl2 and CCl3 are studied. The intrinsic barrier ΔE#BX correlates with the degree of the O-O bond contraction in the transition structure. Both intrinsic and overall barriers can be predicted with the aid of Marcus theory. Progressive degrees of chlorination of the alkyl group in B produce decreases in the barrier to proton transfer from HBCOH+ to OCXH and increases in the reverse transfer barriers. These changes can be quantitatively reproduced by the Marcus equation for all systems.
- Ab initio
- Marcus theory
- Proton-transfer barriers
- Protonated formaldehyde dimer derivatives
ASJC Scopus subject areas