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New Macrocyclic Complexes of Some Transition Metals: Synthesis and Characterization

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New Macrocyclic Complexes of Some Transition Metals: Synthesis and Characterization Al-Azhar University of Gaza Postgraduate Studies and Research Affairs NEW MACROCYCLIC COMPLEXES OF SOME TRANSITION METALS: SYNTHESIS AND CHARACTERIZATION BY GHADA A. MUHANNA SUPERVISOR Prof. Dr. OMAR S. M. NASMAN AL-AZHAR UNIVERSITY-GAZA Submitted In Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry, Faculty of Science, Al-azhar University of Gaza, Palestine. Department of Chemistry, Faculty of Science Al-Azhar University of Gaza GAZA- PALESTINE 2010 I NEW MACROCYCLIC COMPLEXES OF SOME TRANSITION METALS: SYNTHESIS AND CHARACTERIZATION BY GHADA A. MUHANNA 2010 This thesis was defended successfully on ………………….. and approved by Committee Members Signature 1)…………………. …………. 2)…………………. …………. 3)…………………. …………. 4)…………………. …………. II Dedication To MOTHER, BROTHERS, SISTERS, MY FAMILLY, AND TO THE SOUL OF MY FATHER III ACKNOWLEDGEMENTS I would first like to express my deep sense of gratitude to my research supervisor Prof. Dr. Omar Nasman, for his support, guidance throughout the course of this work. I especially would like to acknowledge Al-Azhar University- Gaza, and The Islamic University-Gaza throughout the course of research programme. I wish to thank all my colleagues and friends for their constant support. Finally, I want to thank my husband. He was a test of husband patience. My husband not only endured, he also encouraged, assisted and inspired. IV DECLARATION This thesis is submitted in partial fulfillment of the requirements of the degree of master of chemistry at Al-Azhar University, Gaza. Non of the work presented here has been submitted in support of an application for another degree or qualification at this or any other university or institute of learning. Ghada A. Muhanna Department of chemistry Al-Azhar University of Gaza V ABSTRACT Condensation of o-thiosalicylic acid, with 1,2-ethylenedibromide and ethylenediamine in presence of metal ions gave new types of 14-membered dithiadiazamacrocyclic complexes. The mode of bonding and overall geometry of the complexes has been inferred through UV-vis, IR spectral technique as well as molar conductance and atomic absorption spectra. An octahedral 2+ 2+ 2+ geometry around the metal ions is suggested for [MLX2] (M =Mn , Fe , Co , 2+ 2+ 2+ Ni , Cu , Zn ; X= Cl or NO3). The template condensation reaction of 2-aminobenzoic acid with diethylenetriamine and thiodiglycolic acid in the presence of transition metal ions give new types of 20-membered thiapentazamacrocyclic complexes 2+ 2+ 2+ 2+ 2+ 2+ [ML]X2 (M = Mn , Fe , Co , Ni , Cu , Zn ; X= Cl or NO3). The complexes were characterized by IR, UV-Vis, and 1H NMR spectra as well as molar conductance and atomic absorption spectra. An octahedral geometry around the metal ions is suggested for all the complexes. A new series of 19-membered pentazamacrocyclic complexes has been synthesized by the condensation of 2-amino benzoic acid, phthalaldehyde with diethylenetriamine in ethanol solvent in the presence of transition metal ions and have been characterized through IR, electronic spectral data, conductivity, and atomic absorption. An octahedral geometry around the metal ions has been suggested for the complexes. VI LIST OF TABLES Table (1) Yields, colours, elemental analysis, melting point, and molar conductance values for 14-membered ring of 24 dithiadiazamacrocyclic complexes. Table (2) I.R frequencies (cm-1) for 14-membered ring of dithiadiazamacrocyclic complexes. 25 Table (3) UV spectra for 14-membered ring of dithiadiazamacrocyclic complexes. 26 Table (4) 1H NMR spectroscopic data for 14-membered ring of dithiadiazamacrocyclic complexes. 27 Table (5) Yields, colours, melting point, elemental analysis, and molar conductance values for thiapentaazamacrocyclic complexes 30 Table (6) I.R frequencies (cm-1) for thiapentaazamacrocyclic complexes 31 Table (7) UV spectra for thiapentaazacomplexes 32 Table (8) 1H NMR spectroscopic data for thiapentaazamacrocyclic complexes 33 Table (9) Yields, colours, melting point, elemental analysis, and molar conductance values for pentaazamacrocyclic complexes. 36 Table (10) I.R frequencies (cm-1) for pentaazamacrocyclic complexes. 37 Table (11) UV spectra for pentaazamacrocyclic complexes. 38 Table (12) 1H NMR spectroscopic data for pentaazamacrocyclic complexes 39 VII LIST OF SCHEME Scheme (1) Self-condensation of o-phthalonitrile 6 Scheme (2) Typical in situ synthesis for metal phthalocyanines 8 Scheme (3) Curtis synthesis 9 Scheme (4) Reaction mechanism of 1,2-diaminoethane with acetone 10 Scheme (5) Metal-Free condensation of 1,2-diaminoethane with acetone 10 Scheme (6) Example for macrocycle formation by the kinetic template effect. 11 Scheme (7) Example for macrocycle formation by the thermodynamic template effect. 12 Scheme (8) Condensation reaction of thiosalicylic acid with ethylenediamine and ethylenedibromide in the presence of transition metal ions. 22 Scheme (9) Condensation reaction of 2-aminobenzoic acid with diethylenetriamine and thiodiglycolic acid in the presence of transition metal ions 28 Scheme (10) Condensation reaction of 2-aminobenzoic acid with diethylenetriamine and phthalaldehyde in the presence of transition metal ions 34 VIII TABLE OF CONTENTS CHAPTER ONE INTODUCTION TO MACROCYCLIC COMPLEXES 1-1 Introduction 2 1-2 Design of macrocyclic ligands by coordination Template effect 7 1-3 Types of Template Effect 11 1-4 The anion template effect in the synthesis of macrocycles 12 1-5 Metal – ion selectivity 14 1-6 Template synthesis of mixed thiaazamacrocyclic complexes 18 CHAPTER TWO RESULTS AND DISCUSSION 2-1 Template synthesis and characterization of 14-membered macrocyclic complexes 22 2-2 Template Synthesis and characterization of a new series of 20- membered macrocyclic complexes 28 2-3 Synthesis and characterization of a new series of 19-membered pentaazamacrocyclic complexes 34 CHAPTER THREE EXPERIMNTAL 3-1 Materials and Methods of analysis 41 3-2 Synthesis of 2,11-dioxo-5,8-dithia-1,12-diaza- cyclotetradecane)M(II) chloride/ nitrate 41 3-3 Synthesis of 5,9,12,16-tetraoxo-11-thia-1,4,8,13,17- pentaaza-cyclononadecane)M(II) chloride/nitrate 42 3-4 Synthesis of 10,11;14,15;18,19-tribenzo-1,9-dioxo- 2,5,8,12,17-pentaazacyclononadecan)M(II) dichloride/nitrate 42 REFERENCES …………………………………………… 43 IX CHAPTER 1 Introduction To Macrocyclic Complexes 1 [1.1] Introduction The chemistry of macrocylic complexes has occupied a central role in the development of coordination chemistry. The metal ion and host guest chemistry of macrocyclic ligands has developed rapidly over recent years and now impinges on wide areas of both chemistry and biochemistry. During the past decade there has been a growing interest in the synthesis of multidentate ligands which are illustrated for quadridentate ligands and their complexes. The principal types of multidentate ligands are illustrated for quadridentate ligands,e.g., the tripod (1), the open chain(2), and the closed chain or macrocycle(3). (1) L L L L L L L L L L L L (1) (2) (3) Macrocycles may be single-ring systems, e.g., structures I, II, or multiring systems, e.g., the cryptates (III and IV). The obvious resemblance between a planar metal complex of structure and the prosthetic groups in hemoglobin, chlorophyll and vitamin B12, has stimulated research on the synthesis of macrocycles and on the structure, bonding, and reactions of macrocycle-metal complexes. (1) O O O O S S N N O HN NH HN S S NH N N N N S S O O S S (I) (II) (III) (IV) 2 Macrocyclic ligands are polydentate ligands containing their donor atoms and either incorporated in or, less commonly, attached to a cyclic backbone. As usually defined, macrocyclic ligands contain at least three donor atoms and the macrocyclic ring should consist of a minimum of nine atoms. (2) A very large number of synthetic, as well as many natural, macrocycles have now been studied in considerable depth. A major thrust of many of these studies has been to investigate the unusual properties frequently associated with cyclic ligand complexes. In particular, the investigation of spectral, electrochemical, structural, kinetic, and thermodynamic aspects of macrocyclic complexes have all received considerable attention. (2) Coordination Chemistry of macrocyclic ligands is becoming a major subdivision of inorganic chemistry and undoubtly great interest in this area may continue in the future. The macrocyclic complexes of metal ions are synthesized by the reaction of the required metal ion with the preformed macrocyclic ligands, but there are potential disadvantages in this method. The synthesis of a macrocycle in the free form often results in a low yield of the desird product with side reactions where polymerization is predominating. In order to circumvent this problem, the ring-closure step in the synthesis may be introduced to restrict rotation in the open-chain precursors thereby facilitating cyclization. One effective method for the synthesis of macrocyclic complexes involves an in situ approach wherein the presence of a metal ion in the cyclization reaction markedly increases the yield of the cyclic product.(3) The fact that macrocyclic ligand complexes are involved in a number of fundamental biological systems has long been recognized. (2) 3 The chemistry of macrocyclic ligands has been a fascinating area of current research interest to the chemists all over the world. The continued interest and quest in designing new macrocyclic ligands stem mainly from their use as models for protein-metal binding sites in biological systems, as models for metalloenzymes, as sequestering
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