Titanium Phosphinidene and Phosphide Moieties from Oxidative Phosphorylation and Desilylation

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Coordination Chemistry

Background:

• Mononuclear titanium complexes are versatile synthetic platforms.
• Phosphorus-ligand chemistry offers unique bonding possibilities.
• Understanding Ti-P interactions is crucial for catalysis and materials science.

Purpose of the Study:

• To report the synthesis of novel mononuclear titanium complexes featuring phosphinidene and phosphide ligands.
• To explore new titanium-phosphorus bonding motifs, including multiple bonds.
• To characterize these novel complexes using advanced spectroscopic and structural methods.

Main Methods:

• Reaction of titanium precursors with sodium phosphide and related reagents.
• Oxidative phosphorylation and desilylation reactions.
• Characterization by multinuclear NMR, EPR, and X-ray crystallography.

Main Results:

• Synthesis of a Ti(III) phosphinidene complex [K(crypt)][(PN)2Ti═PSiMe3].
• Formation of a molecular titanium phosphide complex [K(crypt)][(PN)2Ti≡P] featuring a Ti≡P triple bond.
• Generation of a terminal Ti(IV) phosphinidene complex [(PN)2Ti═PSiMe3].
• Structural and spectroscopic characterization of all new complexes.

Conclusions:

• Demonstrated a unique entry into mononuclear titanium complexes with phosphinidene and phosphide ligands.
• Established unprecedented Ti-P bonding, including a Ti≡P triple bond.
• Highlighted the potential for further functionalization and exploration of titanium-phosphorus chemistry.