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

Despite relevance as molecular analogs of binary metal/pnictogen heterogeneous catalysts, late-metal molecular phosphido clusters are scarce. Herein, we describe an entry into copper phosphido and phosphinidiide chemistry leveraging the reducing nature of a prearranged Cu⁰₂Cu^I core. Pnictogen atom capture from Na[PCO] affords the first molecular copper phosphide (<b>2</b>), which is a potent nucleophile. Electrophilic functionalization yields a series of phosphinidiide complexes, including the parent P-H compound (<b>3</b>^<b>H</b>). Electrochemical measurements suggest that <b>2</b> participates in hydrogen atom transfer chemistry; thermochemical benchmarking and reactivity studies support a moderate P-H bond strength of 69.1 kcal/mol for <b>3</b>^<b>H</b>. These findings provide insights into structural characteristics and proton coupled electron transfer reactivity of Cu₃P units, conspicuous structures in copper phosphide heterogeneous catalysis.