White phosphorus activation by a Th(III) complex.

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Elemental phosphorus (P4) is a fundamental allotrope with complex reactivity.
• Thorium organometallic complexes offer unique electronic properties for small molecule activation.
• Understanding P4 activation is crucial for phosphorus chemistry and materials development.

Purpose of the Study:

• To investigate the activation of elemental phosphorus (P4) by a thorium complex.
• To characterize the structure and bonding of the resulting thorium-phosphorus adduct.
• To explore the electronic structure and bonding interactions within the novel P4 binding mode.

Main Methods:

• Synthesis of the thorium complex [Th(Cp'')3] where Cp'' = {C5H3(SiMe3)2-1,3}.
• Reaction of the thorium complex with elemental phosphorus (P4).
• X-ray crystallography for structural determination of the product [{Th(Cp'')3}2(μ-η(1):η(1)-P4)] (1).
• Density Functional Theory (DFT) calculations on a model system to probe bonding.

Main Results:

• Successful activation of P4 by [Th(Cp'')3] to form [{Th(Cp'')3}2(μ-η(1):η(1)-P4)] (1).
• Discovery of an unprecedented cyclo-P4 binding mode coordinated to two thorium centers.
• DFT studies provided insights into the electronic structure and nature of the Th-P bonds.

Conclusions:

• Thorium complexes can effectively activate elemental phosphorus.
• A novel cyclo-P4 structure and binding mode have been synthesized and characterized.
• The findings advance the understanding of phosphorus activation and organothorium chemistry.