Potentially hemilabile imidazolyl- and pyridylphosphine ligands (L) were used to make a new series of gold and copper chlorido complexes (L-M-Cl). The gold monophosphine complexes L-Au-Cl existed as monomers whereas the copper species crystallized as tetramers with halide or phosphine bridging ligands. Yields of all complexes were >88%. Addition of a second equivalent of ligand resulted in reversible formation of L²MCl, which completely converted to two-coordinate species L²M+ when metathesis with a non-coordinating anion was performed. Comparisons of spectral data for L, L-M-Cl, and L²M+ are made, as well as studies on small-molecule binding and activation facilitated by the heterocyclic nitrogens.