Theoretical and spectroscopic study of the effect of ring substitution on the adsorption of anisole on platinum

The adsorption of anisole, 3,5-dimethylanisole, and 3,5-bis-(trifluoromethyl)-anisole on Pt(111) was studied theoretically and compared to the adsorption of benzene using relativistically corrected density functional theory. A cluster of 31 platinum atoms was used to simulate the surface. The three anisoles were found to be less strongly adsorbed than the parent molecule benzene, 3,5-bis-( trifluoromethyl)-anisole showing weakest adsorption, with an adsorption energy of only one-third that of benzene. The theoretical study was complemented by in situ ATR-IR spectroscopy of the adsorption of the anisole derivatives on a polycrystalline Pt film. The spectroscopic study indicated that the adsorption strength of the anisoles follows the same order as predicted by the calculations. In addition, catalytic hydrogenation tests showed that the propensity to aromatic ring hydrogenation can also be correlated to the mode and strength of adsorption of the anisoles. The degree of saturation followed the same order as the adsorption strength found by the calculations and indicated by spectroscopy. Although 3,5-dimethyl substitution on anisole resulted in only a partial loss of adsorption energy and reactivity toward ring hydrogenation as compared to anisole, the substitution by CF3 groups led to a large loss of adsorption energy and complete loss of reactivity toward aromatic ring saturation. Along with the study of the substituent effect on the adsorption of aromatic molecules, the correlation between adsorption and propensity to saturation of aromatic substrates could be corroborated.