Two‐Coordinate Cu(I) and Au(I) Complexes Supported by BICAAC and CAAC Ligands
Krishna K. Manar, Soumyadeep Chakrabortty, Vishal Kumar Porwal, Darsana Prakash, Sandeep Kumar Thakur, Angshuman Roy Choudhury, Sanjay Singh
Abstract
Abstract Two‐coordinate Cu(I) and Au(I) complexes supported by bicyclic (alkyl)(amino)carbene, [BICAAC‐CuCl] ( 1 ), [BICAAC‐CuI] ( 2 ), [(BICAAC) 2 Cu] + [PF 6 ] – ( 3 ) and [(BICAAC) 2 Au] + [AuCl 2 ] – ( 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 KPF 6 gave [(CAAC cy ) 2 Cu] + [PF 6 ] – ( 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] + [CuI 2 ] – ( 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⋯M (M=Cu, Au) and weak non‐covalent C−H⋯X (X=Cl, I) and C−H⋯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.