Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions.

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Actinide Chemistry

Background:

• Multiple bonding in uranium complexes is well-established.
• Thorium complexes with multiple bonds to elements like P are largely unknown due to synthetic challenges and stabilization issues.

Purpose of the Study:

• To synthesize and characterize novel thorium-phosphorus multiple bond complexes.
• To investigate the electronic structure and bonding characteristics of these new actinide complexes.

Main Methods:

• Synthesis of thorium-phosphorus complexes under ambient conditions.
• Structural authentication using X-ray diffraction.
• Computational analysis of electronic structure and bonding.

Main Results:

• Structurally authenticated examples of thorium(IV)-phosphanide, thorium(IV)-phosphinidene, dithorium(IV)-phosphinidiide, and discrete actinide-phosphido complexes were obtained.
• Computational analysis revealed nuanced bonding in thorium, involving 5f, 6d, and 7s orbitals, challenging the traditional view of dominant 6d contributions.

Conclusions:

• This work establishes the first examples of thorium-phosphorus multiple bonds.
• The findings expand the scope of actinide multiple bond chemistry and provide new insights into thorium's electronic structure and bonding.