Synthesis, structural studies and characterisation of new (N2S2)‎ and (N2O2)‎ tetradentate mannich base ligands derived from phosphinic acid with thiosemicarbazide and semicarbazide and their coordination complexes with some metal ions

العناوين الأخرى

تحضير و دراسة تراكيب و تشخيص قواعد مانيخ جديدة رباعية السن من نوع (N2S2)‎ و (N2O2)‎ مشتقة من حامض الفوسفينيك و ثايوسيمي كاربازايد و سيمي كاربازايد و معقداتها التناسقية مع بعض الأيونات الفلزية

مقدم أطروحة جامعية

Muhammad, Ahmad Jasim

مشرف أطروحة جامعية

al-Jabburi, Muhammad Jabir
Abd al-Ghani, Ahlam Jamil

الجامعة

جامعة بغداد

الكلية

كلية العلوم

القسم الأكاديمي

قسم الكيمياء

دولة الجامعة

العراق

الدرجة العلمية

دكتوراه

تاريخ الدرجة العلمية

2007

الملخص الإنجليزي

Four new Mannich base tetradentate ligands with type (N2O2) and (N2S2) have been prepared: bis(thiosemicarbazide methyl) phosphinic acid [H3L1], bis(1–phenylsemicarbazide methyl) phosphinic acid [H3L2], bis(1,4–diphenylsemicarbazide methyl) phosphinic acid [H3L3] and bis(1,4–diphenylthiosemicarbazide methyl) phosphinic acid [H3L4].

Sythesis was carried out by the condensation of phosphinic acid with formaldehyde and thiosemicarbazide[H3L1],1–phenylsemicarbazide[H3L2],1,4-diphenyl semicarbazide [H3L3] and 1,4–diphenylthiosemicarbazide [H3L4] in mole ratios of (1:2:2) respectively.

The reaction has been carried out in acidic medium (6NHCl) at reflux and under nitrogen atmosphere.

The ligands have been characterized and their structures were elucidated depending upon microelemental analysis(CHN), spectral data (I.R, U.V–Vis, 1H, 13C, 31P NMR and mass spectra).

Series of metal complexes of the four ligands with metal ions such as CrIII, MnII, FeII, CoII, NiII, CuII, ZnII, CdII and HgII have been synthesized by heating 1 mmole of each ligand with 1 mmole of metal chloride in refluxing methanol and under nitrogen atmosphere especially for (FeII) and (CoII) complexes using methanolic solution of potassium hydroxide to maintain the pH around (9).

The complexes were characterised and their stereochemical structures and geometries were suggested depending upon data of microelemental analysis (CHN), spectral studies (I.R, UV–Vis, 1HNMR for K[NiII(L1)], and K[ZnII(L4)], Mass spectra for K[CoII(L1)] and K[CuII(L4)] as well as magnetic moments, metal Abstract B content and conductivity measurements.

The following general formula were achieved: K2[CrIII(L)Cl2], K3[M(L)Cl2], where M= Mn(II) and Fe(II) ions, and K[M(L)], where M = Co(II), Ni(II) Cu(II), Zn(II), Cd(II) and Hg(II) ions.

The I.R spectra showed that the ligands were deprotonated in the complexes and behaved as trinegative tetradentate (N2O2) (N2S2) donors in all complexes.

The data of microelemental analysis suggested (1:1) (M:L) molar ratio.

The mass spectra of the complexes K[CoII(L1)] and K[CuII(L4)] proved the four coordinate bonding type of metal ions (Co(II) and Cu(II) with ligand atoms.

The 1HNMR spectra of the complexes K[NiII(L1)] and K[ZnII(L4)] proved that bonding of metal ion occurred with thiol anions.

The electronic spectra in DMF (10–3 M) supported by magnetic moments in solid state revealed octahedral geometries for the Cr(III), Mn(II) and Fe(II) complexes, square planar for the Co(II), Ni(II) and Cu(II) complexes and tetrahedral for the Zn(II), Cd(II) and Hg(II) complexes.

The spectra of both Co(II) and Cu(II) complexes in DMF were indicative of octahedral geometries as a result of further coordination of the metal ions to solvent molecules.

Conductivity measurements of the new synthesized complexes in DMF (10–3 M) showed the electrolytic nature of (1:1) for Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) complexes, (2:1) for Cr(III) complexes and (3:1) for Mn(II) and Fe(II) complexes.

The study of complex formation by molar ratio in DMF solution, has been also investigated and results were supportive to those of solid complexes, where the ratio of (M: L) was (1:1).

التخصصات الرئيسية

الكيمياء

الموضوعات

• العمليات الكيميائية
• التفاعلات الكيميائية

عدد الصفحات

128

قائمة المحتويات

• APA
• MLA
• AMA

لغة النص

الإنجليزية

نوع البيانات

رسائل جامعية

رقم السجل

BIM-600118