Menu

تم مناقشة اطروحة طالبة الدكتوراه (لمى عبد القادر حاتم) اختصاص علوم كيمياء/ كيمياء لاعضوية يوم الثلاثاء الموافق 24/ 12/ 2019 وعلى قاعة كلية العلوم للمناقشات - جامعة تكريت، عن اطروحتها الموسومة (Synthesis, and characterization, of mercury (II) mixed ligand complexes of ortho cyano-amino thio-phenolate or benzotriazole and phosphines or amines, biological study of mercury (II) benzotriazolate phosphines ) وقد تألفت لجنة المناقشة من: 

أ.  د. فالح حسن الموسوي                                                                          (رئيساً)

أ. د. عباس علي صالح                                                                             (عضواً)

أ.  د. ماهر عبد الرزاق                                                                            (عضواً)

أ. د. مظهر يونس مهدي                                                                           (عضواً )

 أ. م. د.احمد عبد الستار ارزوقي                                                                 (عضواً )

 أ. د صبحي عطية محمود                                                                         (عضواً ومشرفاً)

وقد تضمنت اطروحة الطالبة:

 

The present study describes synthesis and characterization of two series of new mercury(II) complexes containing mixed ligands :-The anion 2-cyanoaminothiophenolate and phosphine or amine Ligands . And Hg(II), Pd(II) complexes with benzotriazole containing mixed ligands. All the prepared complexes were characterized by elemental analysis, IR, 1H, 31P-{1H}NMR and some by 13C-{1H}NMR. Some of the prepared complexes were also characterized by X-ray diffraction for single crystals . Chapter One:- Presented a brief introduction to the chemistry, uses of metal ions used in this work (Mercury and Palladium), and a background of amine and phosphine ligands, their interactions with transition metals and applications. The cleavage reactions of heterocyclic ligands by metal ions also were discussed . Chapter Two:- Provided the experimental details for the prepared complexes described in chapter three (Part 1 and 2 ). Part One:- The work is devoted to novel series of synthesis of mixed ligands Hg(II) complexes with 2-cyanoaminothiophenolate (L) and phosphine or amine ligands. Reaction of 1:1 molar ratio of Phenyl mercuric acetate and NaOH as a base with 2-aminobenzothiazole afforded [PhHg(L)] (L=2-cyanoaminothiophenolate). This complex resulted from a deprotonation of the coordinated 2-aminobenzothiazole ligand and insertion of Hg(II) ion into the carbon-sulfur bond . The results confirmed that 2-cyanoaminothiophenolate ligand behaved as a mono dentate ligand bonded to Hg(II) ions via the sulfur atom of thione group to afforded complexes of the type [PhHg(L)], [PhHg(L)(phos)], [[PhHg(L)(diamine)] , these were as following: Reaction of [PhHg(L)] (L= 2-cyanoaminothiophenolate) with monophosphine or its sulfate (monophosphine= PPh3, SPPh3). Treatment of [PhHg(L)] with two moles equivalent PPh3 gave the mononuclear complex [Hg(L)(PPh3)], where L behaved as a monodentate ligand bonded through S to the Hg(II) center. while the SPPh3 ligand where L behaved as a bidentate chelate bonded through S to one Hg(II) center and as a bridging bonded through S atoms towards the second Hg(II) center to give the binuclear complex [PhHgL(SPPh3)]2 . Reaction of the [PhHg(L)] with dppm afforded [PhHgL(dppm)]2 complex, dppm behaved as a bridging bidentate ligand and L ligand behaved as a monodentate ligand bonded through S to Hg(II) center to give a binuclear complex [PhHgL(dppm)]2. Reaction of [PhHg(L)] with dppe gave [PhHgL(dppe)] as a polymer and chelate complexes, dppe behaved as a bidentate chelate ligands bonded to Hg(II) center. And a bridging bidentate ligand, and L ligand behaved as a monodentate ligand bonded through S to Hg(II) to give polymeric complex. Reaction of [PhHg(L)] with dppp or dppb afforded [PhHgL(dppp)] or [PhHgL(dppb)] complexes, dppp, dppb behaved as bidentate chelate ligands bonded to Hg(II) center. Reaction of [PhHg(L)] with dppf gave [PhHgL(dppf)] complex, dppf behaved as a bidentate chelate ligand and L ligand behaved as a monodentate chelate ligand bonded through S to Hg(II) center . The [PhHgL(diamine)] (diamine=bipyridine (Bipy), 1,10-phenonthroline (Phen) or ethylenediamine (en) ligands in a 1:1 molar ratio). The (L) anion, behaves as a monodentate ligand bonded to Hg(II) through S atom, while the Bipy, Phen , ligands behave as bidentate chelate ligands bonded through N atom of the heterocycles ring , and (en) ligand behaved as bidentate chelate ligand toward Hg(II) center . Treatment of [PhHgL] complex with amine ligands produced [PhHgL(Amine)2] complexes (Amine = 2,6-diaminopyridine (dapy), 2-aminpyrimidine (Apmy)). The L ligand behaved as a monodentate ligand , and the amine ligands behaved as a monodentate bonded to Hg(II) ion through the nitrogen atom of the heterocyclic rings to give complexes of the type [PhHgL(Amine)2]. Part Two:- Complexes of the benzotriazole (Hbta) ligand was used to prepare two starting complexes with mercury and palladium divalent ions; [Hg(bta)2] and [Pd(bta)Cl]2 respectively. Moreover, diphosphines {diphos= Ph2P(CH2)nPPh2; n=2, dppe; n=3, dppp} or mono phosphine (PPh3) , (en= ethelendiamine) were used as co-ligands to prepare a series of additive complexes with complex [Hg(bta)2] Thus, the reactions of the complex [Hg(bta)2] with diphosphines in 1:1 mole equivalent ratios were afforded the complexes of the formula [Hg(bta)2(diphos)]; diphos= dppe or dppp . Whereas the complex [Hg(bta)2(PPh3)2] was resulted from the reaction of complex [Hg(bta)2] with two mole equivalents of PPh3. And the reactions of the complex [Hg(bta)2] with en=ethelendiamine in 1:1 mole equivalent ratios were afforded the complex of the formula [Hg(bta)2(en)]; the results prove that benzotriazolate is linked to mercury through its deprotonated nitrogen atom with monodentate fashion. The complexes [Hg(bta)2(diphos)]; diphos= dppe or dppp , or [Hg(bta)2(PPh3)2] were used for studying their hydrogen storage ability after detecting their BET surface area. Furthermore, the thermodynamic parameters were recorded for the H2 storage on complex [Hg(bta)2] . The results show that complex [Hg(bta)2] is able to store 3.35 wt% physically at 77 K under 120 bar. Some of the [Hg(bta)2] complexes were used to examine their ability to prevent two types of bacterial growth, and the results showed antibacterial ability . [Pd(Hbta)2Cl2] complex was deprotonated to form [Pd2(bta)2Cl2] in order to prepare series of P-Pd-bta complexes, the same reactions between the diphosphines and complex [Pd(Hbta)2Cl2] were unsuccessful while the reaction of complex [Pd(Hbta)2Cl2] with two mole equivalents of PPh3 was gave the complex [PdCl(bta)(PPh3)]2.DMSO . the benzotriazole (Hbta) ligand bonded as monodentate ligand through the neutral nitrogen atom in complex [Pd(Hbta)2Cl2] , For complex [PdCl(bta)(PPh3)]2.DMSO structural information exposed that benzotriazole acts as bidentate bridging through deprotonated nitrogen atom and one neutral nitrogen atom , was obtained which it structure confirmed by X-ray diffraction .

lumma24122019 1

lumma24122019 2

 

lumma24122019 3

 

Go to top