Identification of reaction intermediates during hydrogenation of CD 3CN on Raney-Co

Abstract

Reaction intermediates formed on the surface of Raney-Co after co-adsorption of acetonitrile- d 3 (CD 3CN) and hydrogen were investigated by inelastic neutron scattering (INS). Detailed information on the structure of the adsorbed molecules was obtained by comparison of the spectra of potential reaction intermediates with reference spectra of H 2, CD 3CN, and CD 3CH 2NH 2 as well as INS spectra calculated by ab initio methods. We concluded that CD 3CN reacted preferentially with hydrogen bound to η 3 sites on the Co-001 plane. On the surface, a mixture of a nitrene-like intermediate and co-adsorbed CD 3CH 2NH 2 was formed, as indicated by a strong CH 2 twisting vibrational mode, which decreased in intensity relative to the other CH 2 vibrational modes, when the amount of hydrogen was increased. The surface study is complemented with detailed catalyst characterisation as well as kinetic data on the hydrogenation of acetonitrile- d 3 .