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.
2018
Istituto di Chimica dei Composti OrganoMetallici - ICCOM -
Hydrolysis
Phosphites
Platinum
Phosphine
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/376702
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