Catalyst-induced changes in a substituted aromatic: A combined approach via experiment and theory

We report on infra-red absorption and thermal desorption experiments, together with first-principles density functional theory calculations, for anisole adsorbed on single-crystal Pt surfaces. Substantial structural deformations were observed, consistent with major changes in the occupancy of molecular π orbitals. Our results lend insight into electronic effects in catalysed hydrogenolysis of substituted benzyl groups, enabling us to explain our recent observation that anisole fails to exhibit the enhanced reaction rate predicted by conventional wisdom.