Electronic effect of a perfluorinated β-diketiminate ligand on the bonding nature of copper carbonyl complexes. Issue 28 (3rd July 2020)

• Record Type: Journal Article
• Authors: Huse, Kevin; Weinert, Hanns; Wölper, Christoph; Schulz, Stephan
• Is Part Of: Dalton transactions. Volume 49:Issue 28(2020)
• Page Start: 9773
• Page End: 9780
• Publication Date: 2020-07-03
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt01943g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A combined experimental and computational study demonstrates the influence of fluorine substituents on the electronic properties of β-diketiminate ligands. Abstract : Two copper complexes 17 Fnac2 Cu(C6 H6 ) (3 ) and 17 Fnac2 CuCO (4 ) containing the monoanionic, perfluorinated β-diketiminate 17 Fnac2 − ligand (1 ) ( 17 Fnac2 = FC[C(CF3 )N(C6 F5 )]2 ) were synthesized and characterized by IR and NMR spectroscopy ( 1 H, 13 C, 19 F), cyclovaltammometry (CV), elemental analysis and single crystal X-ray diffraction. The perfluorinated 17 Fnac2 − ligand marginally reduces the π-back-bonding capacity of the copper centre to the carbonyl group in 4 when compared with the corresponding 16 Fnac2 − substituted complexes but substantially when compared with the fluorine free substituted derivatives. Quantum chemical calculations gave deeper insight into the bonding situation of this carbonyl complex, while CV studies were performed to determine the oxidation potential of 3 in solution. Based on these data, the influence of the degree of fluorination in different β-diketimine ligands on the electronic nature of the corresponding copper complexes is discussed.