Synthesis,Characterization And Properties Of The Polyamine-Co Oxygenated Complexes By Solid-State Reaction

Oxygen carriers are certain important transition metal complexes which can transform and store dioxygen reveisibly in living bodies. The study on oxygen carriers is of important significance in military and civil applications, especially in the fields of dioxygen separation, metal anti-corrosion and keeping fresh of fn駎s. Recently, solid-state reaction shows its great advantages m coordination chemistxy. It breaks through n馿s of traditional liquid phase reaction and ceitain materials can on be prepared by solid-state reaction. So introduction of solid-state reaction into the rcsearch of transition metal complexes of oxygen cameis would get a new break. To establish this view we have used solid-state reaction method to prepare some cobalt complexes as oxygen carriers, study their oxygenation properties and comparison ⁴th those obtained from classic liquid phase methods. The contents of this work contain five parts: 1 .Recent development of oxygenation of cobalt complexes was reviewed,such as the stnicture and properties of some typical oxygen carriers. Their significance as model of natural oxygen carriers and potential applications in industrial processes were showed. 2.Two cobalt complexes with ethylenediamine(en) and I 2-propane diamine (pn) were prepared by solid-state reaction in room temperature.They could produce superoxo type oxygenated complexes of Co:02 ^l :1 (mole ratio) with 02.The two oxygenated complexes were isolated and characterized by elemental analysis, IR,XRD,TG/DTA and molar conductance. The oxygenation mechanism of solid- state reaction was discussed. 3.Four complexes of Co(Il) with ethylenediamme, drethylenetriamine were synthesized by gas-solid state and nonaqueous solvent reaction separately They show an inert property toward dioxygen and can exist steadily in the air as an unoxygenated complex when they are in solid state while they have a strong reactivity toward dioxygen when they are dissolved in aqueous solution. The same complexes obtained from different methods are paratnorph. Their oxygenation in aqueous solution show that one mole of oxygen is absorbed for every two moles of complex. The non-isothermal kinetics of thermal decomposition in the first step of the en-Co(ll) complex was investigated, the probable mechanism is Zhuralev,Lesokin and Tempelnian Equation,three-dimensional diffusion (global symmetry) and the non-isothermal kinetic equation is da/dt = l.5Ae^1-a((1/(l- 4.Two cobalt complexes with diethylenetriamine(dien), Uiethylenetetramine (trien) were synthesized by solid-state reaction in room temperature. It was foi^md that one mole complex reacts with two mole of dioxygen in room tempé‘¢ature.The reason of exceed oxygen uptake is that the ligand is oxidatively dehydrogenated (- CH2-NH- - -C=N-). Two oxygenated complexes synthesized from solid-state reaction were isolated and characterized by elemental analysis,]R,XRD,TGIDTA and molar conductance.The mechanism that diffiision controls the oxygenated pro- cesses of solid-state was discussed. 5A new complex of 8-aminoquinoline cobalt was prepared by solution and solid-state reaction separately and was characterized by elemental analysis, IR,XRD,TG/DTA and molar conductance.The -NH, is probably oxdized into -NO2 because the 8AQCo could make ² activated.