Phosphites (P(OR)3) are prone to P-O cleavage by hydrolysis, giving heteroatom-substituted phosphine oxides,1 which are widely used for phosphonation reactions2 and the syntheses of phosphoramidates, and phosphanes. Phosphite hydrolysis is generally accelerated under acid and basic reaction conditions. We found that Pt(II) bis-aqua complexes bearing bis-(phosphane)metallocene-based ligands (Scheme 1) were suitable catalysts for the hydrolysis of the first P-O bond of P(OR)3, conducted under neutral reaction condition (i.e. THF/water) at room temperature. In situ NMR spectroscopic studies and DFT calculations shed light on the overall catalytic process.
Catalytic Phosphite Hydrolysis
Oberhauser Werner;Manca Gabriele
2018
Abstract
Phosphites (P(OR)3) are prone to P-O cleavage by hydrolysis, giving heteroatom-substituted phosphine oxides,1 which are widely used for phosphonation reactions2 and the syntheses of phosphoramidates, and phosphanes. Phosphite hydrolysis is generally accelerated under acid and basic reaction conditions. We found that Pt(II) bis-aqua complexes bearing bis-(phosphane)metallocene-based ligands (Scheme 1) were suitable catalysts for the hydrolysis of the first P-O bond of P(OR)3, conducted under neutral reaction condition (i.e. THF/water) at room temperature. In situ NMR spectroscopic studies and DFT calculations shed light on the overall catalytic process.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.


