Synthesis and (spectro)electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives.
نویسندگان
چکیده
Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (1, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of 1 gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1-oxide (2, sulfoxide) and 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1,1-dioxide (3, sulfone), respectively. The molecular structures of 1 and 3 in the solid state were determined by single crystal X-ray crystallography. The oxidation of sulphide 1 to sulfone 3, plays only a minor role on the overall structure of the two compounds. Electrochemical (cyclic voltammetry (= CV), square wave voltammetry (= SWV)) and spectroelectrochemical (in situ UV-Vis/NIR spectroscopy) studies were carried out. The CV and SWV measurements showed that an increase of the sulphur atom oxidation from -2 in 1 to +2 in 3 causes an anodic shift of the ferrocenyl-based oxidation potentials of about 100 mV. The electrochemical oxidation of 1-3 generates mixed-valent cations 1(+)-3(+). These monooxidised species display low-energy electronic absorption bands between 1000 and 3000 nm assigned to IVCT (= Inter-Valence Charge Transfer) electronic transitions. Accordingly, the mixed-valent cations 1(+)-3(+) are classified as weakly coupled class II systems according to Robin and Day.
منابع مشابه
Synthesis, Antimicrobial and Electrochemical Studies of Four Substituted Isatin Derivatives at a Glassy Carbon Electrode
Isatins, derivatives of indole, represent important class of compounds belonging to nitrogen heterocycles. These compounds comprise synthetically vital substrates that are used as precursors for drug synthesis and raw materials for heterocycles etc. Research in this group of compounds has engrossed interest among scientific community in recent and past as Isatins are known to possess immense bi...
متن کامل[FeFe] Hydrogenase: Protonation of {2Fe3S} Systems and Formation of Super-reduced Hydride States**
The synthesis and crystallographic characterization of a complex possessing a well-defined {2Fe3S(μ-H)} core gives access to a paramagnetic bridging hydride with retention of the core geometry. Chemistry of this 35-electron species within the confines of a thin-layer FTIR spectro-electrochemistry cell provides evidence for a unprecedented super-reduced Fe(I)(μ-H)Fe(I) intermediate.
متن کاملEuropean Research Conference: Organic Electrochemistry: Moving towards Clean and Selective Synthesis Industrial Synthesis of Cysteine Derivatives
متن کامل
Synthesis and Molecular Docking Studies of 2-arylideneindan-1,3-diones Derivatives as an Inhibitor of 17β-hydroxysteroid Dehydrogenase Type 1
Due to the drawbacks of applying catalysts in the synthesis of α,β-unsaturated structure units and the importance of these materials, electrochemistry has been introduced as an efficient alternative.Therefore, herein a high-yield synthesis of 2-arylideneindan-1,3-diones is proposed. The procedure is carried out in propanol, using electrons as a green catalyst for generating propanol anion...
متن کاملNew Method of Synthesis of Stable Zero Valent Iron Nanoparticles (Nzvi) by Chelating Agent Diethylene Triamine Penta Acetic Acid (DTPA) and Removal of Radioactive Uranium From Ground Water by using Iron Nanoparticle
Nowdays, iron nanoparticles due to their unique characteristics are used in all of sciences and technology. These nano particles due to their electrical, magnetic, optical and catalytic properties and having high area and activity that is promped by their small size and most importantly many scientists from the entire world are interested in th...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Dalton transactions
دوره 44 13 شماره
صفحات -
تاریخ انتشار 2015