The Study On Synthesis And Voltammetry Properties Of Bridged-Diferrocenyl Compounds

Highly attention to ferrocene, attributing to the unique structure and special properties, taked by researchers. During the past studies,people had good try to the model building, property researching and the further applications, in particular the fields of asymmetric catalysis, materials science, biologically active compounds, the liquid crystal material and electromagnetic device. Our research group has done a lot of work on the electrochemical properties and the design and synthesis of the ferrocene derivatives. In the past years, we have gotten a variety of atom and aromat bridged diferroceneyl or more compounds, at the same time, we have found some difference with the reported findings about channels of electronic interactions in the units and the influencing factor. This article will focus on single heteroatomic bridging and double heteroatomic bridging binuclear ferrocene compounds related to the characteristics of charge transfer. Details are as follows.In this paper, ferrocene used as starting material. Diferroceneyl methane(1) was synthesized by the acid-catalyzed condensation reaction of ferrocene and dimethoxymethane. N, N-diferroceneyl formamide(2) was synthesized by the Cu Ireaction of iodoferrocene, lithium amide and DMF. Using iodioferrocene with anhydrous potassium thiocyanate, catalyzed by CuI, got diferrocenyl sulfide(3). 1, 1-diferroceneyl ethane(4) was synthesized in the route of reducing 1, 2-diferrocenylethanedione with zinc amalgam. Reaction of iodioferrocene with Sodium sulfide nonahydrate, catalyzed by CuI, allowed the formation of 1, 2-diferrocenyldisulfane(5). The single crystal of compound 1, 2, 3, 4 and 5 were cultivated.Characterization of these molecules was performed by FT-IR, 1HNMR, 13 CNMR and MS. The molecular structures were determined by X-ray single crystal diffraction. To the best of our knowledge, compound 2, synthesis of new compounds for the first time and 3 was first structurally synthesized and characterized and never be reported before.In this paper, the electrochemical properties of 1-5 has been tested by cyclic voltammetry and studied based on theoretical calculation and crystalline structure. The results prove that: heteroatomic bridging diferrocene compounds, including1, 2 and 3, show an electronic interaction ability between ferroceneyl units increasing with the decreasing of the dihedral angles of Cp-ring plane, as it to be ?E1/21 ? ?E1/22 ? ?E1/23. For the same atoms bridging of compounds, including 1, 3, 4 and 5, electrochemical comparative analysis of 1 with 3 and 4 with 5 respectively indicated that the spatial distance of ferrocenyl unite was increasing and the electronic interaction ability decreasing with the increasing of bridge atomic amount. The comparition of 4 with 5 showed that 5 had a better electronic interaction ability than 4. In the process of electrochemical analysis, we also found that the first oxidation potential was decreasing with the increasing of Cp-ring, connected with bridging atom, and HOMO of Fe electronic cloud distribution. Under the premise of smilar electron cloud distribution, with the NBO total charge density of Cp-ring and Fe increasing, the oxidation potential was decreasing.