Studies On The Syntheses And Properties Of Dinuclear Metal Complexes And Cyclopalladated Ferrocenylimines

In this thesis, the synthesis of both dinuclear metal complexes and cyclopalladated ferrocenylimines compounds as well as the structure -property relationships were studied in the following two parts:1. A series of ligands with N, O or N, S as election donor atoms and their transition-metal dinuclear complexes were synthesized . The binding abilities of ligands 1, 2, 3, 5 for metal ions were studied by extraction equilibrium and cation transport through bulk liquid membranes.1.1 Six type schiff base polytopic ligands with N, O or N, S as election donor atoms were synthesized by condensing the corresponding l,3-diamino-2-propanol or l,3-bis(o-nitrophenoxy)-2-propanol and different aldehydes, such as 2-hydroxybenzaldehyde, pyridine-2-carboxaldehyde and thiophene-2-carboxaldehyde. Their composition and structure were characterized by elemental analyses, IR, 'H NMR and ljC NMR spectroscopy .The X-ray single crystal structure of ligand 2 was undertaken, and the results obtained established the structure of the kind of ligand.1.2 Transition metal dinuclear complexes of 8-11 were prepared by reacting the appropriate ligands with CuCli, CuBr2, ZnCb etc. in ethanol. The composition and the structure were characterized by elemental analyses, IR and UV spectroscopy. The study of single-crystal X-ray diffraction established the molecular structure of the dinudear Zn( II) complex. Complex 11 crystallized in monoclinic space group p2(l)/n with a=10.035(2)A, b=8.6841(17)A, c=25.666(5) P =101.23(3) deg.,V=2194.0(8) A 3,and Z=4. Refinement gave R=0.0603 and Rw =0.01282 for 4054 observed reflections.1.3 The binding abilities of compounds 1,2,3,4,5 for alkali and alkaline earth and transition-metal cations were evaluated by extraction equilibrium and cation transport through buld liquid membranes. Experiments shown that these ionophores have greater transporting ability for transition-metal cations, such as: Cu( II), Ni( II) and Co( II) compared with Mg( II), K( I), Na( I ),and Li( I )ions. The cation transport rates by ionophores 1,2,3,5 decrease in the order: Cu2+> Ni2+> Co2+ > Na+> Mg2+ > K+. The difference of transport ability of the four compounds was 5 > 2 > 1 > 3 and they all had good selectivities for Cu2+/ Co2+, Ni2+/Co2+, Na~V Mg2+, especially the selectivity coefficient of Cu2+/ Co2+ is as high as 127.97.The selectivity sequences of . the three compounds were also similar, i.e. Cu2+/ Co2+ > Ni2+/ Co2+ > Na+/ Mg2+.2. A series of the cyclopalladium( II) compounds of ferrocene imino-derivative were synthesized and characterized by EA,IR, and 1H NMR spectroscopy, and their properties as a catalyst for catalytic hydrolysis of thiophosphate ester were also studied.2.1 Ferrocenyketimines 12-16 were synthesized by the condensation of acetylferrocene with hydroxylamine hydrochloride, ethanolamine, o-anisidine, w-anisidine and 2-aminophelol respectively.The reactions of ferrocenylketimines with Li2PdCl4 yielded cyclopalladated compounds 17-20. The new compounds obtained were characterized by EA, IR and 1H NMR spectra.2.2 Four functional substituted derivatives of cyclopalladated ferrocenylketimines 17-20 were as mimetics of metal-dependent esterases for catalyzing the hydrolysis of thiophosphoric acid esters pesticides. All the four cyclopalladated complexes could efficiently catalyze the degradation of thiophosphoric acid pesticides, such as methyl parathion. The Pd catalyst with coordinated oxime was more active and exhibited an increased selectivity towards pesticides containing sulfur and the rate of hydrolysis of methyl parathion catalyzed by the cyclopalladated oxime was as high as 850 mAbs/min at pH 8.0.2.3 Take the highest active cyclopalladated ferrocenylketimine 17 as an example, the reaction mechanism has also been studied.