Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions

Area of Science:

• Organometallic Chemistry
• Catalysis
• Phosphorus Chemistry

Background:

• Tertiary phosphites are versatile phosphorus compounds.
• Hydrolysis of phosphites is important for chemical synthesis.
• Efficient catalysts for phosphite hydrolysis are needed.

Purpose of the Study:

• To investigate cationic phosphametallocene-based platinum(II) aqua complexes as precatalysts.
• To achieve selective P-O bond cleavage in phosphite hydrolysis.
• To elucidate the catalytic mechanism.

Main Methods:

• Utilized cationic phosphametallocene-based platinum(II) aqua complexes.
• Performed hydrolysis of aromatic and aliphatic tertiary phosphites.
• Employed NMR labeling, stoichiometric model reactions, and DFT calculations.

Main Results:

• The complexes acted as efficient precatalysts for phosphite hydrolysis.
• Selective cleavage of one P-O bond was achieved under neutral conditions.
• The catalytic cycle involves intramolecular water transfer to cis-coordinated phosphite.

Conclusions:

• Cationic phosphametallocene-based platinum(II) complexes are effective catalysts for phosphite hydrolysis.
• The mechanism involves a unique intramolecular water transfer pathway.
• This study provides mechanistic insights into phosphite P-O bond cleavage.