Electrochemical Study Of Osmacycles, Ruthenacycles, Iridacycles And Related Organic Compounds

Organic electrochemistry is an interdisciplinary subject based on the mutual combination of organic chemistry and electrochemistry,which is closely related to all areas of organic chemistry and electrochemistry.In recent years,impressive progress has been made in research on organic electroanalysis,organic electrosynthesis, organic photoelectrochemistry and organic electrocatalysis.Owing to the demands of materials,energy,information,surrounding and life for organic electrochemistry,as well as the interpenetration of organic chemistry and electrochemistry,organic electrochemistry will have great development prospect.In this dissertation,comprehensive and systematic electrochemistry properties of metal complexes(Osmacycles,Ruthenacycles and Iridacycles) and organic compounds(Cp^- ion and dialdehyde) are investigated.The dissertation contains seven chapters as following:In Chapter 1,the applications of electroanalytical techniques in the transition-metal-containing organometallic complexes are introduced.According to the main objective of this dissertation,the research progress on electroanalysis of mononuclear,binuclear,multinuclear metal complexes is also summarized emphatically.Furthermore,the significance and the process of the electrochemical redox reaction in organic synthesis are presented.Additionally,the research prospect of organic electrochemistry is reviewed.Chapter 2 mainly introduced the experimental methods and devices.The principles of electrochemical technologies,including cyclic votammetry,differential pulse voltammetry,potential step,in-situ electrochemical UV-Vis spectra, constant-current chronopotentialmetry and potentiostatic electrolysis,are described.In Chapter 3,the electrochemical behaviors of ruthenabenzene [Ru(CHC(PPh₃)CHC(PPh₃)CH)Cl₂(PPh₃)₂]Cl and osmabenzene[Os(CHC(PPh₃)CH-C (PPh₃)CH)Cl₂(PPh₃)₂]OH are studied by above-mentioned electrochemical technologies for the first time.The generality and specific characteristics for electrochemical reaction of osmabenzenes and ruthenabenzenes with different substitutions are investigated,and the possible electrochemical reaction mechanisms are proposed.Additionally,redox properties of bridged binuclear and trinuclear osmabenzenes indicate the metal centers interaction through bridging ligands.In Chapter 4,electrochemical study on conjugation-bridged oxa-Iridium six-membered ring dimmer is discussed.Electron transfer process and reaction kinetics parameters are researched.The results show that there is a strong interaction between the two iridium centers.In order to study the electrochemical reaction, controlled potential electrolysis is carded out and the electrolytic products are characterized by NMR and X-ray single crystal diffraction.Chapter 5 describes the electrochemical chlorination of Cp^- ion derivative.The redox property of Cp^- ion derivative is studies by CV.Based on the result of CV,the anodic oxidation is carried out by controlled potential electrolysis.The electrolytic product is separated and purified.Furthermore,chloride Cp^- is obtained and structurally characterized by NMR and X-ray single crystal diffraction.In addition, radical reaction mechanism which is electrically initiated is proposed.In this chapter, chloride Cp^- is prepared by environmentally friendly electrochemical method,which differs from the traditional organic reaction.Chapter 6 mainly studies the synthesis,antioxidation and electrochemical property of a novel glutaraldehyde derivative.Treatment of[Ru(CHC(PPh₃)CHC-(PPh₃) CH)Cl₂(PPh₃)₂]Cl with concentrated nitric acid produces a novel dialdehyde [OHCC(PPh₃)CHC(PPh₃)CHO]NO₃ in high yield.The dialdehyde is stable even in the presence of nitric acid.Reaction of the dialdehyde with fluoboric acid gives [HOCHOCHC(PPh₃)CHC(PPh₃)](BF₄)₂,which is structurally characterized. Electrochemical study on the dialdehyde further confirms the antioxidation property of dialdehyde.Moreover,the reductive process of dialdehyde at -1.71 V is investigated by in-situ electrochemical UV-Vis spectra,which demonstrates that the electron transfer is followed by chemical reaction of the reduced intermediate,namely, an electrochemical(EC) mechanism.In addition,a cyclic anhydride[OC(O)C(PPh₃)-CHC (PPh₃)C(O)]ClO₄ is obtained by electrolysis at high potential(+2.0 V). In Chapter 7,the innovation of the dissertation is concluded and the prospect of this research is presented.