Modeling stabilization of SiO bonds by Pd/Pt complexes using density functional theory

The binding energy of various Pd and Pt complexes to silanones has been studied using the B3LYP density functional method and relativistic effective core potentials. Pt complexes systematically show stronger binding to silanones than their Pd counterparts, particularly with bis-diphosphinoethane ligands. Electron withdrawing substituents on the silanone lead to stronger binding. The metal–silanone interaction appears to be a pure three-center bond, with electron donation from metal to silicon and back-donation from oxygen to metal. The (CF3)2SiOPt(DMPE) complex appears to be a good synthetic target for the generation of protected silanones.