![](/images/graphics-bg.png)
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
Other Title(s)
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
Dissertant
Thesis advisor
al-Jabburi, Muhammad Jabir
Abd al-Ghani, Ahlam Jamil
University
University of Baghdad
Faculty
College of Science
Department
Chemistry Department
University Country
Iraq
Degree
Ph.D.
Degree Date
2007
English Abstract
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).
Main Subjects
Topics
No. of Pages
128
Table of Contents
Table of contents.
Abstract.
Abstract in Arabic.
Chapter One : Introduction.
Chapter Two : Experimental part.
Chapter Three : Results and discussion.
References.
American Psychological Association (APA)
Muhammad, Ahmad Jasim. (2007). 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. (Doctoral dissertations Theses and Dissertations Master). University of Baghdad, Iraq
https://search.emarefa.net/detail/BIM-600118
Modern Language Association (MLA)
Muhammad, Ahmad Jasim. 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. (Doctoral dissertations Theses and Dissertations Master). University of Baghdad. (2007).
https://search.emarefa.net/detail/BIM-600118
American Medical Association (AMA)
Muhammad, Ahmad Jasim. (2007). 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. (Doctoral dissertations Theses and Dissertations Master). University of Baghdad, Iraq
https://search.emarefa.net/detail/BIM-600118
Language
English
Data Type
Arab Theses
Record ID
BIM-600118