Dinuclear copper(I) complexes with N-heterocyclic thione and selone ligands: synthesis, characterization, and electrochemical studies

The synthesis, characterization, and structures of a series of homoleptic and heteroleptic copper(I) complexes supported by N-heterocyclic chalcogenone ligands is reported herein. The quasi-reversible Cu(II/I) reduction potentials of these copper complexes with monodentate (dmit or dmise) and/or bidentate (Bmm(Me), Bsem(Me), Bme(Me), Bsee(Me)) chalcogenone ligands are highly dependent upon the nature and number of the donor groups and can be tuned over a 470 mV range (-369 to 102 mV). Copper-selone complexes have more negative Cu(II/I) reduction potentials relative to their thione analogs by an average of 137 mV, and increasing the number of methylene units linking the heterocyclic rings in the bidentate ligands results in more negative reduction potentials for their copper complexes. This ability to tune the copper reduction potentials over a wide range has potential applications in synthetic and industrial catalysis as well as the understanding of important biological processes such as electron transfer in blue copper proteins and respiration.