A Molecular Tricopper Phosphide: Synthesis, Functionalization, and Hydrogen Atom Abstraction.

Area of Science:

• Inorganic Chemistry
• Catalysis Science

Background:

• Late-metal molecular phosphido clusters are scarce despite their relevance as analogs for heterogeneous catalysts.
• Copper phosphide structures are important in copper phosphide heterogeneous catalysis.

Purpose of the Study:

• To explore copper phosphido and phosphinidiide chemistry.
• To synthesize and characterize novel copper-phosphorus compounds.
• To investigate their potential in catalysis.

Main Methods:

• Utilizing a prearranged Cu2CuI core for pnictogen atom capture.
• Employing electrophilic functionalization for derivative synthesis.
• Conducting electrochemical measurements and thermochemical benchmarking.

Main Results:

• Synthesized the first molecular copper phosphide (2) and a series of phosphinidiide complexes, including the parent P-H compound (3H).
• Demonstrated that compound 2 is a potent nucleophile and participates in hydrogen atom transfer.
• Determined a moderate P-H bond strength of 69.1 kcal/mol for 3H.

Conclusions:

• Established a new route to copper phosphido and phosphinidiide chemistry.
• Provided insights into the structural and proton-coupled electron transfer reactivity of Cu3P units.
• Highlighted the relevance of these molecular compounds as models for heterogeneous copper phosphide catalysts.