Selective phosphanyl complex trapping using TEMPO. Synthesis and reactivity of P-functional P-nitroxyl phosphane...

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Radical Chemistry

Background:

• Organophosphorus compounds are crucial in various chemical applications.
• Open-shell species offer unique reactivity and electronic properties.
• Tungsten phosphanido complexes serve as versatile precursors.

Purpose of the Study:

• To synthesize and characterize novel open-shell phosphanyl complexes.
• To investigate the trapping of these complexes with TEMPO.
• To explore the formation and properties of P-nitroxyl phosphane complexes, including the P-F variant.

Main Methods:

• One-electron oxidation of lithium phosphanido complexes.
• Trapping reactions with TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl).
• Thermolysis of P-nitroxyl phosphane complexes.
• Theoretical investigation of reaction pathways.

Main Results:

• Successful synthesis of open-shell phosphanyl complexes (OC)5W{(Me3Si)2HCP(X)} (X = F, H).
• Formation of thermally labile P-nitroxyl phosphane complexes via TEMPO trapping.
• First experimental evidence for an open-shell P-F phosphanoxyl complex, (OC)5W{(Me3Si)2HCP(O)F}, obtained through thermolysis.
• Theoretical studies elucidated reaction mechanisms.

Conclusions:

• Open-shell phosphanyl complexes can be effectively generated and stabilized.
• TEMPO is a viable trapping agent for these reactive species.
• The discovery of the P-F phosphanoxyl complex expands the scope of radical phosphorus chemistry.