Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η⁵-C₅H₄)(η⁵-C₅H₅); R = H, 5; Bu, 7; CH₂CH₂(OCH₂CH₂)₂OMe, 9), [M(κ²O,O'-FcC(O)CHC(O)Fc)_n] (M = Ti, n = 3, 10; M = Fe, n = 3, 11; M = BF₂, n = 1, 12), and 1-R'-3,5-Fc₂-C₃HN₂ (R' = H, 13; Me, 14; Ph, 15) is discussed. The solid-state structures of 5, 7, 9, 12, 13, 15, and 16 ([TiCl₂(κ²O,O'-PhC(O)CHC(O)Ph)₂]) show that 7 and 9 exist in their β-diketo form. Compound 13 crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule. The electrochemical behavior of 5-7 and 9-16 was studied by cyclic and square-wave voltammetry, showing that the ferrocenyls can separately be oxidized reversibly between -50 and 750 mV (5-7, 9, 12-15: two Fc-related events; 10, 11: six events, being partially superimposed). For complex 10, Ti-centered reversible redox processes appear at -985 (Ti^II/Ti^III) and -520 mV (Ti^III/Ti^IV). Spectro-electrochemical UV-Vis/NIR measurements were carried out on 5, 6, and 12, whereby only 12 showed an IVCT (intervalence charge-transfer) band of considerable strength (ν = 6250 cm^-1, Δν = 4725 cm^-1, ε = 240 L·mol^-1·cm^-1), due to the rigid C₃O₂B cycle, enlarging the coupling strength between the Fc groups.