Two-Coordinate Cu(I) and Au(I) Complexes Supported by BICAAC and CAAC Ligands

摘要

abstract_textpTwo-coordinate Cu(I) and Au(I) complexes supported by bicyclic (alkyl)(amino)carbene, [BICAAC-CuCl] (1), [BICAAC-CuI] (2), [(BICAAC)(2)Cu](+)[PF6](-) (3) and [(BICAAC)(2)Au](+)[AuCl2](-) (6) have been synthesized. The reaction of cyclic (alkyl)(amino)carbene, CAAC(cy)with CuCl afforded [CAAC(cy)-CuCl] (4) and its further reaction with KPF6 gave [(CAAC(cy))(2)Cu](+)[PF6](-) (5). Complexes 1-6 have been characterized by multinuclear NMR, IR and UV-Vis., spectroscopic method and high-resolution mass spectrometry (HRMS). Single crystal X-ray structure of heteroleptic complexes 1 and 4 and homoleptic complexes [(BICAAC)(2)Cu](+)[CuI2](-)(2'), 3 and 6 have also been determined. The crystal structure of these complexes confirmed linear two-coordinate geometry around the metal centers. In the solid- state, complexes 1,2',4 and 6 displayed C-H center dot center dot center dot M (M=Cu, Au) and weak non-covalent C-H center dot center dot center dot X (X=Cl, I) and C-H center dot center dot center dot H-C interactions. Computational calculations correlate well to the experimentally observed geometry and help elucidate the absorption characteristics type of transitions and the frontier orbitals involved in them./p/abstract_text