Activation of P₄ and P₂ by Transition Metal Complexes at Room Temperature

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Phosphorus Chemistry

Background:

• Diphosphinidene ligands (P2) are rare in coordination chemistry.
• Exploring novel ligand types is crucial for advancing synthetic chemistry.

Purpose of the Study:

• To synthesize and characterize the first complex with a P2 ligand acting as an eight-electron donor.
• To investigate the reactivity of a novel Re2P2 butterfly complex.

Main Methods:

• Reaction of [Cp*(OC)2Re]2 with P4 at room temperature.
• Subsequent reaction of the Re2P2 butterfly by-product with [W(CO)5(thf)].
• Characterization of the resulting multinuclear complexes.

Main Results:

• Formation of the first complex with an eight-electron donor diphosphinidene ligand (1).
• Synthesis of a Re2P2 butterfly complex as a reaction by-product.
• Generation of two new multinuclear complexes, including a ReWP2 tetrahedrane framework and a planar Re2P2W2 complex (2).
• Transformation of the P2 ligand into two µ-P ligands in complex 2.

Conclusions:

• The study demonstrates the successful synthesis of unprecedented organometallic complexes featuring diphosphinidene ligands.
• The reactivity of the Re2P2 butterfly complex highlights its versatility in forming complex multinuclear structures.
• These findings expand the scope of phosphorus-based ligands in coordination chemistry.