THEORETICAL-STUDIES OF CARBOCATIONS ADSORBED OVER A LARGE ZEOLITE CLUSTER - IMPLICATIONS ON HYDRIDE TRANSFER-REACTIONS

A semiempirical MNDO study of simple alkylcarbenium ions (Me, Et, i-Pr , t-Bu) on a large and more realistic cluster, comprising a hexagonal prism and a sodalite unit (3) and simulating different adsorption site s on zeolite Y, was carried out. On going from H to bulky alkyl groups , there is an increasing tendency to stretch the Al-O bond length and to decrease the Si-O-Al bond angle. Nevertheless, the proton and the a lkyl groups are covalently bonded to the framework, as expressed by th e high bond orders, near unity. Adsorption on site O-4, located in the sodalite, is energetically disfavored by 2-4 kcal/mol relative to ads orption on site O-1, in the hexagonal prism. The MNDO calculations on cluster 3 showed a reasonable agreement with ab initio calculations of carbenium ions adsorbed on smaller clusters 1 and 2, except when adso rption on O-4 is considered, indicating that steric strain, due to the crystalline structure, plays an important role. Adsorption on Si-O-Si sites is about 45 kcal/mol higher in energy than the correspondent ad sorption on Si-O-Al sites. This result may explain the observed experi mental dependence of hydride transfer reactions with the structural Si /Al ratio, also suggesting the participation of the zeolite structure in the transition state.