aNHC-Stabilized Low-Valent Phosphorus Compound: Exploring Dual Catalytic Activity via Nucleophilicity and P(I)/P(III)...

Area of Science:

• Organometallic Chemistry
• Catalysis
• Materials Science

Background:

• Low-valent phosphorus compounds are valuable synthetic intermediates.
• Stabilization of reactive phosphorus species is crucial for their application.
• N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry.

Purpose of the Study:

• To synthesize and characterize a novel mesoionic N-heterocyclic phosphinidene (mNHP).
• To investigate the electronic structure and bonding of the mNHP.
• To explore the nucleophilic and redox reactivity of mNHP.
• To evaluate mNHP as a metal-free catalyst.

Main Methods:

• Synthesis and characterization of mNHP.
• Natural resonance theory analysis.
• Single-crystal X-ray diffraction.
• Reactions with CO2, CS2, and C(Ar)-F bonds.
• Spectroscopic studies (XPS).
• Density Functional Theory (DFT) calculations.

Main Results:

• Successful synthesis and structural confirmation of mNHP, a P(I) species with two lone pairs.
• Demonstrated nucleophilic reactivity with CO2 and CS2.
• Exhibited redox behavior via oxidative addition to a C(Ar)-F bond, forming a P(III) species.
• mNHP functions as a metal-free catalyst for thiol formylation and hydrodefluorination.

Conclusions:

• mNHP is a stable, low-valent phosphorus compound with accessible lone pairs.
• The compound displays versatile nucleophilic and redox reactivity.
• mNHP serves as an effective metal-free catalyst for key organic transformations.
• This work expands the scope of phosphorus-based catalysis.