Dicationic copper(I) complexes bearing ENE (E = S, Se) pincer ligands; catalytic applications in regioselective cyclization of 1,6-diynes.

Two novel dicationic binuclear Cu(I) complexes of the type [{(BPPP)E}Cu][BF] (E = S (3a); Se (3b)) bearing (BPPP)E (BPPP = bis(diphenylphosphino)pyridine) pincer systems were isolated, and structurally characterized. The solid-state structures of 3a/3b display the presence of intermolecular cuprophilic (Cu⋯Cu) interactions between the two monocationic species, and consist of weak Cu⋯S bonding between the two cations. Besides, complex 3a was introduced as a molecular copper(I) catalyst in cyclization reactions, and new protocols were developed for the synthesis of a series of new oxazole and triazole derivatives bearing alkyne-phenyl propargylic ether substituents. 3a was also found to be active in achieving these two classes of heterocyclic compounds by the mechanical grinding method. One of the key intermediate copper-azide species was detected by the high-resolution mass spectrometry technique, which supports the proposed catalytic pathway. All the reported transformations were accomplished sustainably by employing a well-defined, earth-abundant, and cheap copper(I) catalytic system.