The Original Coordination Chemistry of 2‑Phosphaphenol with Copper(I) and Gold(I) Halides

2-Phosphaphenol (L) forms unusual complexes with copper and gold halides. With CuCl, a dimeric [L<sub>2</sub>CuCl]<sub>2</sub> complex is observed with L acting both as η<sup>1</sup>-P terminal and μ<sub>2</sub>-P bridging ligand and a copper–copper short contact of 2.549 Å. With copper bromide, a distorted infinite chain [L<sub>2</sub>CuBr]<sub><i>n</i></sub> is formed, whereas with copper iodide, the zigzag chain [L<sub>2</sub>CuI]<sub><i>n</i></sub> is observed. The phosphaphenol acts as a terminal ligand coating the CuX molecular wires. With gold chloride, a dimeric [LAuCl]<sub>2</sub> complex is formed, which is held by an aurophilic interaction at 3.132 Å.