Studies On The Syntheses, Electrochemical Properties Of Ferrocene Derivatives

In this thesis, three series of twenty new single-, double-, multi-ferrocenes derivatives containing oxygen, nitrogen, hetero-atoms and also four super molecule compounds of calix[4]arene have been synthesized,. Among these compounds, single crystals of nine ferrocene derivatives, one binuclear copper complex and three super molecules have been obtained and characterized by X-ray structural determination. The composition and construction of these compounds are determined by elemental analysis, 1R, ¹H NMR spectra and X-ray diffraction. Electrochemical properties of some ferrocenes derivatives have been determined. We also studied the liquid-liquid extraction of Au(III) by calix[4]arene.1. Synthesis of the compoundsTwenty new compounds containing single-, multi-ferrocenes derivatives have been synthesized. Four supermolecules [NaL]+[AuXn]^- of calix[4]arene with gold have been obtained by pre-organized extraction. Single crystals of nine ferrocene derivatives, one ferrocenylphenylformic copper complex and three supermolecules have been synthesized for determination. The construction and composition of the compounds are characterized by elemental analysis, IR, ¹H NMR spectra and X-ray diffraction.bond exists in compound 1, forming one-dimensional chain structure. Intramolecular hydrogen bonds exist in compounds 2, 3, 4a, 5a, 6a, 8a. Compounds 2 and 6a feature helical shape, and two ferrocenyl groups located at the two end of the molecule respectively. The dihedral angles between the phenyl ring and plane of cyclopentadienyl ring are difference in above compounds. Three ferrocenyl groups of compound 11c are at the molecular fringe forming tripod structure. Complex 12 forms paddle-wheel-type binuclear-copper complex containing four ferrocenylphenyl groups. The structures of the supermolecules 13 consist of two parts, cationic complex [NaL]+ and anionic complex [AuXn]^- in cationic complex [NaL]+, Na+ lies between the two planes formed by four ether oxygen atoms and four carbonyl oxygen atoms of calix[4]arene, forming a lipophilic cations. Au(III) is sp3 hybrid, forming quadrangle structure [AuX4]- with halogen, and linear structure [AuI₂]^- with iodine for the redox reaction. Since the distance between the gold atom and sodium atom is very long, the cationic complex [NaL]+ and anionic complex [AuXn] are linked by electrostatic attraction to form supermolecule.3. Electrochemical researchElectrochemical properties of compounds 1, 4(4a, 4b), S(5a, 5b), 8a have been investigated by cyclic voltammetry. Kinetic parameters of these compounds are also determined. The redox properties of the ferrocene are not changed after connected with benzene, but it would be influenced by the different substitutions on the phenyl ring. At higher potential values, the phenyl ring and cyclopentadienyl ring may form a huge conjugate system to take part, in the reaction such as compound 4a. When forming complex as complex 12, the redox potential of ferrocene shows little shift, the interactions between the ferrocene and the metal atom are very small because of the phenyl ring. The oxidation of the hydroxybenylidene (compound 5) causes the passivation on the electrode, and made the disappearance the reversible peaks of Fc+/Fc. The redox potential of compound 8a is anodically shifted upon the increasing of [H+], this is because of the protonation of amines. At same time, for the coordinating atoms near the ferrocenyl group, compound 8a gives very large electrochamical shifts for the2. X-ray structure determinationSingle crystal structures of compounds 1, 2, 3, 4a, 5a, 6a, 8a, 10a, lie, 12 and surpermolecules 13a, 13c, 13d are determined by X-ray diffraction. Weak interactions and spatial configurations of the compounds are studied. An intermolecular hydrogentransition metal ions of Zn2+> Cu2"\ Ni2+, and little for Mg2+ and Ca2+. So compound 8a could form 1:1 complexes with the transition metals and be a good receptor of the transition metal ions.4. The liquid -liquid extraction of Au(III) by calix[4]areneIn the presence of the certain amount of sodium ions, the pre-organized cations complex [NaL]+ could extract Au(III) cation quantitatively from the aqueous phase into organic phase in the form of [AuX4]\ The extracted reaction may be expressed as following:Na+(a) +AuX4^a +L(0) = NaLAuX4(0)The equilibrium constant KeX and thermodynamic constants AH0, AS0 have been determined. The results indicate that the system could extract Au(III) with high selectivity in 99% with the presence of sodium ion. The presence of large amount of other cations, such as Mg2+, Ba2+, Mn2+, Co2+, Ni2+, Zn2+ do not interfere with the extraction. Four superamolecules 13a(NaLAuCL0, 13b(NaLAuBr4), 13c[NaLAu(SCN)4], 13d(NaLAul2) were synthesized by extraction, and three of them are determined by X-ray diffraction.