Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Area of Science:

• Organometallic Chemistry
• Uranium Chemistry
• Phosphorus Chemistry

Background:

• Uranium complexes with bulky ligands are key to exploring f-block reactivity.
• Terminal phosphide and phosphinidene complexes are synthetically challenging.

Purpose of the Study:

• To synthesize and characterize novel uranium-phosphine complexes.
• To investigate the bonding in f-block phosphinidene complexes.

Main Methods:

• Reaction of a uranium precursor with sodium phosphide.
• Deprotonation of a uranium phosphide complex.
• X-ray crystallography.
• Density Functional Theory (DFT) calculations.

Main Results:

• Synthesis of a terminal parent phosphide complex [U(Tren(TIPS))(PH2)].
• Synthesis of an unprecedented metal-stabilized terminal parent phosphinidene complex [U(Tren(TIPS))(PH)].
• DFT calculations confirmed a polarized-covalent U-P bond with a Mayer bond order of 1.92.

Conclusions:

• The study demonstrates a new route to f-block phosphinidene complexes.
• The findings provide insights into the electronic structure and bonding of uranium-phosphorus bonds.