Theoretical model for oxidative activation of the O-H bond to platinum(0) complexes

A density functional study has been used to investigate potential energy surfaces of the oxidative addition reaction PtL2 + H-OCH3 --> PtL2(H)(OCH3) (L = CO, PH3, L-2 = H2PCH2PH2, H2PCH2CH2PH2). The B3LYP/LANL2DZ results suggest that a smaller L-M-L angle and a better electron-donating ligand should promote oxidative addition of the O-H bond of CH3OH. In contrast, a linear structure and a better electron-withdrawing ligand would be a good candidate for methanol elimination. (C) 1998 Elsevier Science B.V.