Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions

Cationic phosphametallocene-based
platinum(II) aqua complexes were used as efficient
precatalysts for the hydrolysis of aromatic and aliphatic
tertiary phosphites under neutral reaction conditions at
room temperature, leading to the selective cleavage of one
P-O bond of the phosphite. NMR labeling experiments
combined with stoichiometric model reactions and
theoretical density functional theory calculations, performed
with the appropriate model compounds, shed light
on the operative catalytic cycle, which comprises intramolecular
water molecule transfer to the cis-coordinated
phosphite molecule.