Intramolecular C-H Bond Activation To Construct Ferrocenyl Cyclosulfide And Cyclosulfoxide And Their Applications In Ion Recognition

In this paper,we mainly studied the synthesis and application of cyclothioether and cyclonesulfoxide containing ferrocenyl group.In the first part,a series of containing ferrocenyl cyclosulfide and containing ferrocenyl cyclosulfoxide compounds were synthesized and characterized by various methods.In the second part,containing ferrocenyl cyclosulfide and containing ferrocenyl cyclosulfoxide compounds were used as chemical sensors to study the selective recognition ability for metal ions.In the first part,a series of ferrocenyl o-bromophenyl sulfide compounds were synthesized by the reaction of ferrocenyl-hydrazone with o-bromophenol derivatives.A series of ferrocenyl-containing o-bromophenyl sulfoxide compounds were obtained by simple oxidation of ferrocenyl o-bromophenyl sulfide.containing ferrocenyl cyclosulfide and cyclosulfoxide compounds were obtained by catalyzing intramolecular the C-H bond activation of ferrocenyl o-bromophenyl sulfide and sulfoxide respectively with palladium and phosphine ligands.By optimizing the reaction conditions,the optimal reaction conditions were determined and the yield of the target product up to 80%,and the ee value of contain ferrocenyl cyclosulfide reached 45%.The final product was characterized by nuclear magnetic resonance（NMR）,high resolution mass spectrometry（HR-MS）and single crystal diffraction.In the second part,containing ferrocenyl cyclosulfide and cyclosulfoxide compounds were used as chemosensors to detect metal ions,and fourteen metal ions were identified by UV absorption visible spectrum and electrochemical CV,DPV.The test results showed that both compounds could detect Cu²⁺,and the recognition effect could be visible to the naked eye:Color of ligand solution changed from light yellow to dark green or light green after Cu²⁺was added.The Benesi-Hildebrand equation was used to calculate the detection limit and the complexation constant of the corresponding compound:the lowest detection line of4a was 9.9×10^-7 M,and the complexation constant was 4.926×10⁴ M^-1.The lowest detection line of 6a was 9.6×10^-7 M,and the complexation constant was7.188×10⁴ M^-1.