Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties

The reactions of CuX(2) (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX(2)L(1)](2) (X = Cl (1), Br (2), L(1) = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX(2))(2)L(2)]n (X = Cl (3), Br (4), L(2) = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 1–2 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L(2). All complexes contain a binuclear fragment {Cu(2)(μ-X)(2×2)} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-N(ax) distance is elongated compared to Cu-N(eq). The EPR spectra of compounds 1–4 in CH(3)CN confirm their paramagnetic nature due to the d(9) electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µ(eff) ≈ 1.87 and 1.83 µ(B) (per each Cu(2+) ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µ(B)). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu(2)(μ-X)(2)X(2)} (X = Cl, Br) dimers (J/k(B) ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µ(eff) ≈ 1.72 and 1.70 µ(B) for 3 and 4, respectively, and weak antiferromagnetic interactions (θ ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 1–4 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.