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

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

NEW MACROCYCLIC COMPLEXES OF SOME TRANSITION METALS: SYNTHESIS AND CHARACTERIZATION

GHADA A. MUHANNA

2010

This thesis was defended successfully on ………………….. and approved by

Committee Members Signature

1)…………………. …………. 2)…………………. …………. 3)…………………. …………. 4)…………………. ………….

Dedication

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.

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

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.

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

CHAPTER 1

Introduction To Macrocyclic Complexes

[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)

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)

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 reagents for specific metal ions, as models to study the magnetic exchange phenomena, as chemical sensors and battries, as therapeutic reagents for the treatment of metal intoxication, as medical imaging agents, as catalysts, and in biomedical and fuel cell applications.(3)

The porphyrin ring (4) of the iron-containing haem proteins and the related chlorin (5) complex of magnesium in chlorophyll, together with the corrin ring (6) of vitamin B12 have all been studied for many years.(4,5,6)

R R

NH N NH N

N HN N HN

R R

R (4) R (5)

The synthesis of macrocycles was unsuccessful and wasteful endeavor for many years because of the low yields, the many side products of the reactions, and the large volumes of solvents that were required to give sufficient dilution to minimize polymerization and encourage cyclization. (7)

N N

NH N

(6)

Phthalocyanine (7) and its derivatives bear a strong structural resemblance to the natural porphyrin systems.

NH N N N N HN

(7)

The extensive metal-ion chemistry of phthalocyanine ligands is both interesting and varied. For example, specific phthalocyanines have been shown to behave as semiconductors, as catalysts for a variety of chemical transformations, and have been involved in model studies for a number of biochemical systems. Moreover phthalocyanines and related derivatives have been the subject of intense research because of their commercial importance as colouring agents. Thus phthalocyanine and its substituted derivatives have found widespread use as both blue and blue-green pigments and dyes.(8)

Apart from their intense colours, the complexes also exhibit marked resistance to degredation (they show high thermal stability, fastness to light, and inertness towards acids and alkalis). All these properties favor the use of these compounds as pigments and dyes.(8)

Recognition of the importance of complexes containing macrocyclic ligands has led to considerable effort being invested in developing reliable and inexpensive synthetic routes for these compounds. These macrocycles which contain varying combinations of aza(N), oxa(O), phospha(P) and sulfa (S) ligating atoms can be tailored to accommodate specific metal ions by the fine tuning of ligand design features, such as the macrocyclic hole size, nature of the ligand donors, donor set, donor array, ligand conjugation, ligand substitution, number and sizes of the chelate rings, ligand flexibility and nature

5 of the ligand backbone. The different type of macrocyclic ligands are particulary exciting because of the importance in generating new areas of fundamental chemistry and many opportunities of applied chemistry. The majority of macrocycles represent creative and focused efforts to design molecules which will have particular uses.(3)

The metal ion may direct the condensation preferentially to cyclic rather than polymeric products “the kinetic template effect” or stabilize the macrocycle once formed “ the thermodynamic template effect”

One of the first examples of metal salts facilitating the formation of macrocycle was the self-condensation of o-phthalonitrile to give metal phthalocyanin complexes from which the free ligand was easily displaced as shown in scheme (1). (9)

N CN + 2+ 3+ N 4 M/ M / M / M N N M N CN N N

M =Na, Mg, Cu, Ni, and Sb N M+ =Na+, K+, and Cu+ M2+= Ca2+, Mg2+, Ni2+, and Cu2+ M3+= Fe3+

Scheme (1): Self- condensation of o-phthalonitrile

The role of the metal ions in promoting cyclization was not understood until much later when Hurley et al. isolated a series of intermediate in the reaction between 1,3-diiminoisoindoline with nickel chloride. The widespread utilization of metal ions in the synthesis of macrocycles was developed largely through the work of the group led by Busch. The formation of macrocycles using Ni(II) ions and complexes, led Busch to recognize that the coordination

6 sphere of the metal ion would hold the reacting groups in the correct positions for cyclization reaction, the metal ion acts as a “template”. (1)

R HN S R O C C Ni2+ Ni C + 2 (HSCH2CH2NH2) R HN S C R O

[1.2] Design of Macrocyclic Ligands by Coordination Template Effect:

A brief account of the various design and synthetic strategies developed by investigators in various laboratories to synthesize different macrocyclic complexes is needed for versatile ligand systems with requisite ligand design features. The design of ligands capable of forming stable complexes would not only allow further study of the coordination properties of the different metal ions but would also enable chemists to exploit more fully certain important emerging properties of these complexes. The coordination template effect provides a general strategy for the synthesis of a wide variety of discrete metal complexes. The exciting aspect of this chemistry is that in the majority of cases the molecules meet the design criteria in a sufficient way. It is evident that in an increasing number of cases the driving force behind the synthetic effort is the desire to create a molecule, which will enable the user to make specific applications.(6)

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 desired product with side reaction where polymerization is predominating.(10) In order to circumvent this problem, the ring-closure step in the synthesis may be carried out under conditions of high dilution (11)or a rigid group may be introduced to restrict

7 rotation in the open chain precursors thereby facilitating cyclization.(12) One effective method for the synthesis of macrocyclic complexes involve an in situ approach wherein the presence of a metal ion in the cyclization reaction markedly increases the yield of the cyclic product.(8) The effect of metal ions in promoting certain cyclization reactions was initially discovered when the dark blue complex of the macrocycle was obtained by a template reaction in 1928 as a side product formed during the preparation of phthalimide by reaction of phthalic anhydride and ammonia in an iron vessel.(8,13) This dark blue compound was later shown to be an Fe(II) complex of the highly conjugated macrocycle phthalocyanine (7) which, as mentioned before, bears a strong structural resemblance to the natural porphyrine systems. Since initial discovery, a variety of in situ methods have been employed to prepare phthalocyanine complexes, although there is no single method which can be used for all complexes. Common procedures have involved the reaction between phthalonitrile (or derivative) and a finely divided metal, metal hydride, metal oxide, or metal chloride in either the absence or the presence of solvent, see scheme (2).(2)

CN CN M 4 + 4 + MX2 CN 250C CN boiling No Solvent quinoline Metal Phthalocyanine boiling 250C trichlorobenzene No Solvent boiling formamide O

CONH2 4 NH MX + M O + Urea + 2 CN catalyst MX + 4 NH + 2 O

Scheme (2): Typical in situ synthesis for metal phthalocyanines

Under the conditions mentioned above, the required complexes are very often formed in high yield reflecting the ease with which the cyclization reaction proceeds; however, details of the template role of the metal of such syntheses remain little understood.(14)

A part from this reaction type, the routine use of metal template procedures for obtaining a wide range of macrocyclic systems stems from 1960 when Curtis discovered a template reaction for obtaining apair of isomerism Ni(II) macrocyclic complexes. In Curtis synthesis, a yellow crystalline product 2+ was observed to result from the reaction of [ Ni (1,2- diaminoethane)2] and dry acetone as shown in scheme (3).(15)

H 2 H2 H N N O N N Ni Ni N N N N H2 H2 H

(I)

H H N N Ni N N

(II) Scheme (3): Curtis synthesis

The yellow product was subsequently shown to be a mixture of the the isomeric macrocyclic complexes (I) and (II) in scheme(3).

In this remarkable cyclization reaction, formation of the bridges between the two 1,2-diaminoethane moieties condensation of two acetone molecules per bridge.(16)

Although the sequence of the reaction steps remains uncertain, the mechanism may involve the nucleophilic attack of an acetonyl carbanion on the carbon of coordinated imine as in scheme (4)

CH 3 CH CH 3 3 H2C CH3 CH3 O CH O 3 CH 3 H C NH 2 - H2O N H+ 3 NH O Ni Ni Ni NH 2 NH2 NH2

Scheme(4): Reaction mechanism of 1,2-diaminoethane with acetone

Condensation of the carbonyl function with an amine from a second 1,2- diaminoethane molecule coupled with a repeat of the initial reaction sequence will lead to the cyclic product. It is of interest that this is one case in which the synthesis will also proceed in the absence of a metal ion. Starting from a mono- protonated salt of 1,2-diaminoethane in acetone, the metal-free condensation may proceed via a reaction such as in Scheme (5). Once again, a hydrogen- bonding network may act as a template for the reaction and also serve to stabilize the product once formed. The metal-free ligand (8) has been synthesis(17), in this case the trans-diene ligand was isolated, for example, in greater than 80% yield, as its dihydrobromide.

CH3 2 CH CH3 H 3 CH3 CH3

CH3 N NH H O CH3 N

O H

NH2 NH + H H

N + H H O N H NH CH3 NH2 CH3 NH2 CH H3C 3 CH3 CH3

(8)

Scheme (5): Metal-Free condensation of 1,2-diaminoethane with acetone

[1.3] Types of Template Effect A. KINETIC A reaction is described as proceeding by a kinetic template effect if it provides a route to a product that would not be formed in the absence of the metal ion and where the metal ion acts by coordinating the reactants, as shown in scheme (6).

NaOH NiCl2 + 2H2NCH2CH2SH solution H2N S Ni

H2N S

O CH3

H3C C N S Ni

C N S

H3C

H3C C N S Ni Br2 C N S

H3C

Scheme(6) : Example of macrocycle formation by the kinetic template effect

B. THERMODYNAMIC Macrocycles formed by reactions that are described as proceeding by the thermodynamic template effect can take place in the absence of metal ion.(1)

NH2 O

N NH O H NH

3 H+ +H

N CLO NH H O

N H N

H H N H N

Scheme (7): Example of macrocycle formation by the thermodynamic template effect

[1.4] The anion template effect in the synthesis of macrocycles:-

As an alternate to the metal template synthesis of macrocycles the metal- free ligand can be synthesized by an acid-catalyzed condensation. Sessler et al. have synthesized pyrrole-containing macrocycles (8) and(9) by the acid-catalyzed Schiff base condensation of diformyltripyrrane with 1,2- diamino-benzene or 1,4-diaminobutane, respectively.(18)

N N H N H N NH NH N H N H N N

(9) (10)

When the reaction was carried out in the presence of basic metal salts, such as BaCO3, as a potential template, no product could be isolated if the reaction was carried out in boiling benzene or methanol in the absence of a catalyst. However, (9) and (10) are obtained in high yields when the Shciff base condensation is effected in the presence of stoichiometric quantities of 2+ larger cations such as UO2 or Pb , provided that an acid catalyst is also employed.(32) In an attempt to synthesize the Schiff base macrocycle (11) in the free form the condensation of 3,4-diethylpyrrole-2,5-dicarboxaldehyde with 4,5-diamino-1,2-dimethoxybenzene was carried out by Sessler et al., in the presence of HCl or HNO3. Quantitative yields were obtained when HNO3 rather than HCl was used as the acid catalyst. Under these conditions the free ligand was isolated as a protonated nitrate salt. This nitrate salt on washing (19) with aqueous NaHCO3 produced the free ligand (11).

N MeO N H N OMe

MeO N H N OMe N

(11) This method of synthesizing novel macrocycle by the acid-catalyzed Schiff base condensation led to suggest a general "anion template effect".

[1.5] Metal-ion selectivity:

The macrocycles which contain varying combinations of aza(N), oxa (O), phospha (P), and sulfa (S) ligating atoms can be tailored to accommodate specific metal ions by the fine-tuning of the ligand design features, such as the macrocyclic hole size (cavity size), nature of the ligand donors, donor set, donor array, ligand conjugation, ligand substitution, number and sizes of the chelate rings, ligand flexibility and nature of the ligand backbone.(1,20)

There has been much interest in macrocyclic ligands for use as metal- ion selective reagents a part from the usual parameters influencing the metal- ion specificity of open-chain ligands (such as backbond structure and donor atom type).(2)

By this means, a mechanism for discrimination of ions on the basis of their radii may become available, Although studies of this type are of considerable intrinsic interest, they also have implications for a number of areas. These include: aspects of ion storage and transport in vivo, the solvent extraction of metals from leach solutions in hydrometallurgy, the synthesis of new chromatographic materials for separation of metal ions and the development of metal-ion selective reagents for use in a wide range of analytical, industrial and other applications.(2)

The following discussion focuses on some of the macrocycle factors that are affecting the metal ion selectivity.

14 i) The match between the cation and macrocycle cavity dimensions (cavity size)

The match between the cation and macrocycle cavity dimensions is especially evident in small preorganized(21) macrocycles such as cryptands, calixarenes, spherands, cavitands, porphyrins, etc. These macrocyles have small and rigid cavities and their possible conformational changes upon complexation are very limited. Recently synthesized small aza cages illustrate this point.(22,23) Characteristics common to all of these aza cages are their high molecular preorganiztion which confers unusual basicity behavior, and the presence of small cavities which allow selective encapsulation of metal ions of appropriate size. (22,23) Most of them select and strongly bind the small Li+ ion. The best Li+ binder of the series, the azacryptand (12), shows a regular coordination geometry, coupled with short Li-N bonds (2.06A) all of which indicate an extremely good match between the cation and the cavity radii.(22)

CH3

N X N

CH3 X=NCH3 (12) ii) Conformational rigidity or flexibility:- Conformational rigidity or flexibility of macrocycles has a significant influence on their selective behavior.(24) The comparison of complexing behavior of (13) and (14) where both ligands have the same sets of donor atoms in the rings shows that the complexes formed with 13 are generally more

15 stable. Howevere, the larger and more flexible 14 has a much greater selective behavior toward the same series of metal ions.(25)

H COOH H COOH

N N N N

N N O O COOH HOOC

(14) (13) iii) The number, kind, and arrangement of donor atoms:- The number, kind, and arrangement of donor atoms in the macrocyclic rings also play an important role in macrocycle selectivities. Oxygen donor atoms in crown ethers have the largest affinities for alkali, alkaline-earth, and lanthanide, ions; nitrogen donor atoms favor transition metal ions; and sulfur donor atoms interact preferentially with Ag+, Pb+, and Hg2+.(24) Tertiary amine nitrogen donor atoms form more stable complexes with Ag+ than do secondary amine nitrogen donor atoms. (26) iv) Substituents incorporated into macrocyclic flexible rings:-

Substituents incorporated into macrocyclic flexible rings lead to their stiffening and may alter both macrocycle binding strength and selectivity. Examples are macrocycles containing sugar moieties,i.e., structure (15) compared to the unsubstituted structure (16), in which structure (15-Na+) complex is less stable than structure (16-Na+) complex. This phenomenon may be attributed to the fact that structure (16) ring is flexible, while in the case of structure (15) the glucopyranoside unit makes the crown ring rigid and thus hinders complex formation.(27)

H H OC N O O 3 H O O O H N N H

O O O O O O H N

H (16) (15) C6H5

v) Variation and arrangements of side arms:- Variations and arrangements of side arms, which cooperate with the macrocycle ring in the complexation process, can modify the selectivities of macrocycles. Hancock, for example, observed that the addition of side arms containing neutral oxygen donor atoms to a ligand leads to an increase in selectivity of the ligand for large metal ions over small metal ions and allows the design of ligands with desired selectivities.(28) It was noted that the inductive effect of the side-arm alkyl group increases the electron density on the donor atoms of the macrocycle causing an increase of complex stability but the steric hindrance effect produced by the alkyl group decreases complex stability.(29)

vi) Chelate ring size:- Chelate ring size rather than size-match selectivity may, in some cases, control both stability of complex formation and selectivity of ligands for metal ions, Hancock and luckay examined complexation of Ni2+, Cu2+, Zn2+, Cd2+, 2+ and Pb with the ligands (9) aneN4 through (13)aneN4(structures 17-21) and found that the overall stability patterns of these macrocycles do not accord with the idea of a size-match phenomenon but, in general, the selectivity is controlled by the size of the chelate ring. The results obtained by several different scientific groups indicate that 13-membered chelate rings prefer small

17 metal ions, whereas large metal ions are preferred by 12-membered chelate rings.(30-32)

H N H H H H N N N N

H N N H

N N N N H H H H N H (17) (18) (19)

H H N N H H N N

N N H H N N H H (20) (21)

[1.6] Template Synthesis of mixed thiaazamacrocyclic Complexes:-

Macrocyclic complexes are best prepared with the aid of metal ions as templates to direct the steric course of condensation reaction which ultimately ends with ring closure.(16,20,33) Condensation reaction between carbonyl compounds and primary amines have played a central role in the synthesis of new macrocyclic ligands.(10,34) Usually, reactions are conducted in the presence of a suitable metal ion which serve to direct the condensation preferentially to cyclic rather than oligomeric/ polymeric products – "the kinetic template effect", or to stabilize the macrocycle once formed – "the thermodynamic template effect".(10)

A variety of research has been concerned with the synthetic, and structural aspects of thioazamacrocyclic ligands and their complexes.(35-37) These ligands are of interest as they offer coordination of both hard σ- donor N-ligands and soft σ-donor and potential π-acceptor S-ligands.(38,39) Generally, polyamides or mixed thioazamacrocyclic complexes are prepared by the reaction of a polyamine with either the dicarboxylic acid or the dicarboxylic acid chloride.(40-42) Lindoy and co-workers have reported(43-45) a series of elegant studies on ligand design and metal ion recognition of polyaza and mixed polyazamacrocyclic complexes by convenient non-template methods that do not involve amide groups. Recent studies on macrocyclic complexes containing mixed nitrogen, sulfur, and/or oxygen as donor atoms in the ring systems, which were obtained by the template condensation reaction, show that it remains an active area of research.(46) Recently, Nasman has reported the synthesis of diaza- dioxa,(46,47,48)diaza-dithia,(49,50) and triaza-dioxa macrocyclic complexes(51). In this work, the synthesis of 14-membered ring of dithiadiazamacrocyclic complexes derived from the condensation of o-thiosalcylic acid with 1,2-dibromoethane and 1,2-diaminoethane, in the presence of some transition metal ions are reported. In addition, the synthesis of 20-membered ring of thiapentaazamacrocyclic complexes derived from the condensation of 2- aminobenzoic acid with diethylenetriamine and thiodiglycolic acid, in the presence of some transition metal ions are reported. Finally the synthesis of 19-membered ring of pentaazamacrocyclic complexes derived from the condensation of 2-aminobenzoic acid with diethylenetriamine and phthalaldehyde in the presence of some transition metal ions are also reported.

All of these complexes may have wider applicability. It’s likely prove useful for investigation of metal containing biological molecules such as metalloenzymes, and their catalytic activity for industry(52).

CHAPTER 2

RESULTS AND DISCUSSION

[2.1] Template Synthesis and characterization of 14-membered ring

(N2S2) A new series of 14-membered ring of dithiadiazamacrocyclic complexes were prepared by the template condensation reaction of o-thiosalicylic acid with 1,2-dibromoethane, and 1,2-diaminoethane in ethanol solvent in presence some transition ions, as shown in Scheme (8).

COOH 2 + SH Br Br

O O

OH HO

S S

(I)MX2.nH2O M= Co+2 , Ni+2 , Zn+2, Cu+2 , and Fe+2 (II)

NH2 NH2

O O X NH NH

S S X

Scheme ( 8 ): Condensation reaction of o-thiosalicylic acid with 1,2-diaminoethan and 1,2-dibromoethan

All the complexes have high melting points (>200C0). The results of elemental analysis (Table 1) supports the proposed macrocyclic structure. The molar conductivity values (Table 1) for all complexes in DMSO suggest that they have nonelectrolytic nature.(53) The infrared spectra of the complexes (Table 2) do not exibit any bands characteristic for the free SH or NH2 groups, and the appearance of four new bands characteristic of amide groups(54) in the regions 1651-1698, 1560-1591, and 1219-1282 cm-1, assignable to amide I [ν(C═O)], amide II [ ν(C-N) + δ(N- H)], and amide III [δ(N-H)] bands, respectively, support the macrocyclic structure. A single sharp band observed in the region 3133- 3313 cm-1 may be assigned to ν(N-H) amide group.(55) An important feature is the appearance of a new medium intensity band at 430- 485 cm-1 attributable to ν(M-N) which provides strong evidence for the involvement of nitrogen in coordination.(55) Bands appeared in the 1407-1453, 1020-1036, and 717-751 cm-1 regions are the usual modes of disubstituted benzene. The electronic spectral data (Table 3) off all complexes exhibit absorption in the region 27619-33557 cm-1 which mean that d-d transition, and π – π* transition suggesting an octahedral environment around the metal ions.(56) The 1H NMR spectra of zinc complexes do not show any signal corresponding to alcoholic protons. However, 1H NMR spectrum provides a signal at 8.35 ppm, which is assigned to amide(HN-CO) protons(57). Another signal appeared at 3.39 ppm, (58) corresponding to the methylene protons (CO-N-CH2) which are adjacent to the nitrogen atoms. Furthermore, a signal at 2.43 ppm were observed assignable to methylene protons (CH2-S) which are adjacent to the sulfur atom. and signal appeared at 7.22 ppm assigned to aromatic ring protons.

Table (1) Yields, Colors, Elemental analysis, Melting point, and Molar conductance values of the compounds.

Compound % Color (Found)Calc.(%) m.p ΛΜ yield M C H N Cl (cm2 Ω- 1mol-1) [MnLCl2] 60 Pale pink (9.9)10 (44.6)44.6 (3.7)3.7 (5.5)5.6 (14.6)14.6 220 16 [MnL(NO3)2] 55 Pale pink (10)10.2 (40.1)40.2 (3.4)3.4 (10.3)10.4 - 219 13 [FeLCl2] 50 Brown (10)10.1 (44.5)44.6 (3.6)3.6 (5.7)5.8 (14.5)14.6 240 19 [FeL(NO3)2] 55 Brown (10.3)10.4 (40.1)40.1 (3.3)3.3 (10.3)10.4 - 235 20 [NiLCl2] 55 Pale Mauve (10.6)10.6 (44.2)44.3 (3.7)3.7 (5.7)5.7 (14.5)14.5 245 21 [NiL(NO3)2] 50 Pale Mauve (10.8)10.8 (39.9)40 (3.3)3.3 (10.3)10.4 - 240 25 [CuLCl2] 67 Pale White (12.8)12.9 (43.8)43.9 (3.6)3.7 (5.7)5.7 (14.3)14.4 209 18 [CuL(NO3)2] 65 Pale White (11.5)11.6 (39.9)40 (3.2)3.3 (10.2)10.3 - 215 22 [ZnLCl2] 63 White (11.5)11.6 (43.6)43.7 (3.6)3.6 (5.6)5.7 (14.3)14.4 220 30 [ZnL(NO3)2] 55 White (11.9)11.9 (39.4)39.5 (3.2)3.3 (10.2)10.2 - 218 32

Table (2) I.R. frequencies (cm-1) of the compounds.

Compounds ν (N — H) Amide bands ν (C—H) ν (M—N) Ring vibration Amide I II III [MnLCl2] 3200 1681 1587 1271 2972 475 1453,1035,741 [MnL(NO3)2] 3189 1672 1579 1268 2963 485 1436,1031,740 [FeLCl2] 3176 1691 1591 1282 2356 473 1410,1028,721 [FeL(NO3)2] 3165 1685 1587 1279 2349 469 1407,1025,718 [NiLCl2] 3133 1651 1579 1224 2812 482 1429,1020,717 [NiL(NO3)2] 3105 1659 1560 1219 2920 470 1431,1029,726 [CuLCl2] 3313 1691 1591 1282 2356 430 1417,1035,738 [CuL(NO3)2] 3346 1658 1568 1279 2599 439 1427,1033,731 [ZnLCl2] 3192 1691 1579 1240 2880 469 1421,1036,751 [ZnL(NO3)2] 3273 1698 1581 1282 2915 478 1437,1032,742

Table (3) UV spectral data of the compounds.

Compounds Electronic spectral data λmax (cm-1) [MnLCl2] 33557 [MnL(NO3)2] 33548 [FeLCl2] 27624 [FeL(NO3)2] 27619 [NiLCl2] 32154 [NiL(NO3)2] 32149 [CuLCl2] 32206 [CuL(NO3)2] 32202 [ZnLCl2] 32467 [ZnL(NO3)2] 32461

Table (4) 1H NMR spectroscopic data of the compounds.

Compound CO-NH CO-N-CH2 S-CH2 ring

[ZnLCl2] 8.35 3.39 2.43 7.22

Chemical shift (ppm)

[2.2]Template Synthesis and characterization of 20- membered ring (N5S) A new series of 20- membered ring have been prepared by the condensation of 2-amino benzoic acid with diethylenetriamine and thiodiglycolic acid in ethanol solvent in the presence transition metal ions as shown in Scheme (9):

COOH + 2 NH NH2 NH 2 NH2

O O HN

NH HN

NH2 H2N

OH OH i- M+2 S M= Co+2 , Ni+2 , ii- Zn+2,Cu+2 , and Fe+2 O O

O O +2 NH

NH NH X-2 M

NH S NH

O O

Scheme (9): Condensation reaction of 2-amino benzoic acid with diethylenetriamine and thiodiglycolic acid

All the reactions have low yield, and the complexes have high melting points (< 2300 C). The elemental analysis (Table5) support the proposed structure. The molar conductivity values (table5) for all complexes of in DMSO suggest a (1:2) electrolytic nature.(53) The I.R spectra of all complexes (Table 6) show four bands appeared in the regions (1678-1720), (1535-1580), (1250-1281) cm-1 assignable to amide I [ν (C═O)], amide II [ ν (C-N) + δ (N-H)], and amide III [δ (N-H)] bands, respectively, which support the macrocyclic structure. Furthermore the band appeared at 3319-3413cm-1 assignable to amide ν (N-H), Bands appeared in the (1421-1456), (1015-1035), (721-745) cm-1 regions are the usual modes of disubstituted benzene. An important feature is the appearance of a new band of medium intensity at (449-482) cm-1 attributable to ν (M-N) which provide strong evidence for the involvement of nitrogen in coordination.(59)

The electronic spectral data (Table 7) of all complexes exhibit absorption bands in the region 29933-30303 cm-1 which mean that d-d transition, and π – π* transition suggesting an Octahydral environment around the metal ions.(56)

The 1H NMR spectra doesn't show any signal corresponding to –NH2 or –OH protons. However, show in (Table 8) signal at 8.44 ppm,assigned to amide(51) (CO-NH) protons.(57) Another signal appeared at 2.58 ppm which is assigned

(S-CH2-CO) protons. The signal appeared at 3.84 ppm, corresponding to the (58) methylene protons (CH2-N-CO) protons. The signal at 3.26 ppm assigned to

(C-CH2-NH) protons. Another signal appeared at 6.77 ppm assigned to the secondary amino (C-NH-C) protons of the diethylenetriamine. and 2.17 ppm assigned to (CO-CH2). Furthermore a signal at 7.22 ppm assigned to benzene ring.

Table (5) Yields, Colors, Elemental analysis, Melting points, and Molar conductance values of the compounds.

Compound % Colors (Found) Calc.% m.p ΛΜ (cm2 Ω- M C H N Cl 1mol-1) [MnL]Cl2 50 Pale pink (9.9)10 (48)48.1 (4.5)4.6 (12.7)12.8 (12.8)12.9 258 95 [MnL](NO3)2 53 Pale pink (9.1)9.1 (43.8)43.9 (4.1)4.1 (23.3)23.3 - 255 92 [FeL]Cl2 60 Brown (10)10.1 (48)48 (4.5)4.5 (12.7)12.7 (12.9)12.9 240 88 [FeL](NO3)2 65 Brown (9.2)9.3 (43.7)43.8 (4.1)4.1 (23.2)23.2 - 250 88 [CoL]Cl2 62 Yellowish brown (10.6)10.6 (47.7)47.7 (4.5)4.5 (12.6)12.7 (12.1)12.1 245 103 [CoL](NO3)2 64 Yellowish brown (9.6)9.7 (43.5)43.6 (4.1)4.1 (23.1)23.1 - 243 105 [NiL]Cl2 67 Mauve (10.5)10.6 (47.7)47.8 (4.5)4.5 (12.6)12.7 (12.7)12.8 238 90 [NiL](NO3)2 50 Mauve (9.6)9.7 (43.5)43.6 (4.1)4.1 (23)23.1 - 235 93 [CuL]Cl2 60 Pale green (11.2)11.3 (47.3)47.4 (4.4)4.5 (12.5)12.6 (12.7)12.7 270 107 [CuL](NO3)2 65 Pale green (10.4)10.4 (43.2)43.2 (4)4.1 (22.9)22.9 - 270 102 [ZnL]Cl2 55 Yellowish brown (11.6)11.7 (47.1)47.2 (4.4)4.5 (12.5)12.5 (12.6)12.7 246 87 [ZnL](NO3)2 50 Yellowish brown (10.6)10.7 (43.1)43.1 (4)4.1 (22.8)22.9 - 250 87

Table (6) I.R. frequencies (cm-1) of the compounds.

Compound ν (N — H) Amide bands Ring vibration ν (M—N) Amide I II III [MnL]Cl2 3413 1689 1540 1265 1456,1035,740 470 [MnL](NO3)2 3339 1678 1535 1261 1448,1031,736 478 [FeL]Cl2 3329 1709 1556 1262 1425,1028,737 456 [FeL](NO3)2 3325 1702 1563 1267 1431,1031,728 453 [CoL]Cl2 3413 1681 1578 1261 1444,1025,731 449 [CoL](NO3)2 3338 1679 1571 1265 1439,1022,725 458 [NiL]Cl2 3325 1692 1560 1281 1435,1027,734 482 [NiL](NO3)2 3321 1687 1550 1276 1447,1033,745 479 [CuL]Cl2 3410 1701 1580 1259 1421,1025,739 465 [CuL](NO3)2 3331 1695 1573 1257 1431,1029,741 457 [ZnL]Cl2 3323 1720 1569 1250 1443,1037,744 465 [ZnL](NO3)2 3319 1715 1563 1258 1412,1015,721 472

Table (7) UV spectral data of the compounds.

Compound Electronic spectral data λmax (cm-1) [MnL]Cl2 29980 [MnL](NO3)2 29975 [FeL]Cl2 29979 [FeL](NO3)2 29960 [CoL]Cl2 30075 [CoL](NO3)2 30103 [NiL]Cl2 30075 [NiL](NO3)2 30069 [CuL]Cl2 29940 [CuL](NO3)2 29933 [ZnL]Cl2 30303 [ZnL](NO3)2 30303

Table (8) 1H NMR spectroscopic data of the compounds.

Compound CO-NH C-NH-CO C-CH2-NH S-CH2-CO CH2-N-CH2 CO-CH2 Ring

[ZnL]Cl2 8.44 3.84 3.26 2.58 6.77 2.17 7.22

Chemical shift (ppm)

[2.3] Synthesis and characterization of a new series of 19-membered ring A new series of 19-membered ring have been prepared by condensation of 2- amino benzoic acid, with diethylenetrianine and phthalaldehyde in ethanol solvent in the presence metal ions as shown in Scheme (10).

COOH

2 + NH2 NH NH2 NH2

O O N H

NH HN

NH2 H2N

CHO i- M+2 M= Co+2 , Ni+2 , ii- Zn+2,Cu+2 , and Fe+2 CHO

+ O NH O

NH NH

N N X

[ML1X]X X= Cl or NO3

Scheme (10 ):Condensation reaction of 2-amino benzoic acid with diethylenetriamine and phthalaldehyde

All the complexes (Table 9) have high melting points (>2000C). The results of elemental analysis (Table 9) supports the proposed macrocyclic structure.the molar conductivity values for all the complexes in DMSO suggest a 1:1 electrolytic nature. The IR spectra of all complexes (Table 10) show the absence of uncondenced functional groups (OH, and primary NH2) of the starting materials. However four bands appeared in the regions 1608-1689,1543-1564, and 1215-1298cm-1, assignable to amide I [ν (C═O)], amide II [ ν (C-N) + δ (N-H)], and amide III [δ (N-H)] bands, respectively, which support the macrocyclic structure.(47) furthermore, the band appeared at 3215-3290cm-1 may reasonably be assigned to (N-H) of amide group, and another band at 3080-3165cm-1 assigned to (N- H) of diethylenetriamine. Bands appeared in the regions 1408-1450, 1025- 1045, 726-739 cm-1, are the usual modes of disubstituted benzene. The electronic spectral data (Table 11) off all complexes exhibit absorption in the region 29850-30959cm-1 which means d-d transition, and π – π* transition suggesting an octahydral environment around the metal ions.(56) The 1H NMR spectra of DDPT do not show any signal corresponding to primary amine and /or alcoholic protons. The spectra of the zinc (II) complex (Table 12) show a signal at 8.28 ppm corresponding to the macrocyclic amide (CO-NH) protons(57). A signal at 3.57 ppm corresponding to (CH2-N-CO) protons. Furthermore, a signal appeared at

3.16 ppm can be assigned to (CH2-C-N) protons. Another signal at 6.77ppm reasonably be assigned to the secondary amino(C-NH-C)protons of the diethylenetriamine. A signal at 8.42 ppm assigned to (CH=N) protons(46), and signal at 7.32 ppm corresponding to benzene ring.

Table (9) Yields, Colors, Elemental analysis, Melting points, and Molar conductance values of the compounds.

Compound % Color (Found)Calc.(%) m.p ΛΜ yield M C H N Cl (cm2 Ω- 1mol-1) [MnLCl]Cl 65 Pale pink (9.7)9.7 (55.2)55.3 (4.3)4.4 (12.3)12.4 (12.7)12.8 300 67 [MnL(NO3)]NO3 63 Pale pink (8.8)8.9 (50.4)50.5 (4)4 (22.6)22.7 --- 300 68 [FeLCl]Cl 60 Brown (9.8)9.9 (55.1)55.2 (4.3)4.4 (12.3)12.4 (12.7)12.8 300 65 [FeL(NO3)]NO3 50 Brown (9)9 (50.3)50.4 (4)4 (22.6)22.6 - 300 63 [CoLCl]Cl 45 Yellow (10.3)10.4 (54.8)54.9 (4.3)4.4 (12.2)12.3 (12.6)12.7 180 66 [CoL(NO3)]NO3 40 Yellow (9.4)9.5 (50)50.2 (4)4 (22.4)22.5 --- 200 67 [NiLCl]Cl 69 Mauve (10.3)10.3 (54.9)55 (4.3)4.4 (12.2)12.3 (12.6)12.7 255 64.8 [NiL(NO3)]NO3 50 Mauve (9.4)9.4 (50.1)50.2 (3.9)4 (22.4)22.5 --- 250 63 [CuLCl]Cl 50 Light green (11)11.1 (54.4)54.5 (4.3)4.3 (12.1)12.2 (12.4)12.5 210 63 [CuL(NO3)]NO3 40 Light green (10.1)10.1 (49.6)49.8 (3.9)4 (22.3)22.3 --- 225 66 [ZnLCl]Cl 56 Yellowish (11.3)11.4 (54.2)54.3 (4.3)4.4 (12.1)12.2 (12.5)12.5 255 61 brown [ZnL(NO3)]NO3 51 Yellowish (10.4)10.4 (49.5)49.7 (3.9)4 (22.2)22.3 --- 240 62 brown

Table (10) I.R. frequencies (cm-1) of the compounds.

Compound ν (N — H) Amide bands ν (N — H) Amide I II III [CoLCl]Cl 3215 1689 1554 1259 3110 [CoL(NO3)]NO3 3235 1676 1543 1253 3125 [NiLCl]Cl 3262 1678 1564 1298 3091 [NiL(NO3)]NO3 3265 1685 1544 1282 3080 [CuLCl]Cl 3290 1632 1558 1220 3165 [CuL(NO3)]NO3 3288 1610 1558 1215 3159 [ZnLCl]Cl 3283 1632 1557 1274 3126 [ZnL(NO3)]NO3 3270 1608 1562 1282 3119

Table (11) UV spectral data of the compounds.

Compounds Electronic spectral data λmax (cm-1) [MnLCl]Cl 29985 [MnL(NO3)]NO3 29992 [CuLCl]Cl 30120 [CuL(NO3)]NO3 30090 [NiLCl]Cl 30959 [NiL(NO3)]NO3 30870 [ZnLCl]Cl 30395 [ZnL(NO3)]NO3 30370 [FeLCl]Cl 30010 [FeL(NO3)]NO3 30085 [CoLCl]Cl 29850 [CoL(NO3)]NO3 30050

Table (12) 1H NMR spectroscopic data of the compounds.

Compound CO-NH CH2-N-CO CH2-C-N C-NH-C CH=N Ring

[ZnLCl]Cl 8.28 3.57 3.16 6.77 8.42 7.32

Chemical shift (ppm)

CHAPTER 3

EXPERIMENTAL

[3.1] Materials and Methods of analysis:-

Elemental analyses were obtained from the Micro-Analytical Laboratory. Metals were determined by Atomic absorption spectrometer. Chlorides were determined gravimetrically. IR spectra (4000–200 cm–1) were recorded as KBr discs on Shimadzo FTIR–8201 PC spectrophotometer.

NMR spectra were recorded in DMSO-d6 using a JEOL–JNM– LA300NMR spectrometer with tetramethyl silane as an internal standard. Electronic spectra of the compounds in DMSO were recorded on UV– 1601 UV–Vis spectrophotometer at room temperature. The electrical conductivities of 10–3 M solutions in DMSO were obtained using AC13CM–30V conductivity meter at 25oC.

The metal salts CoCl2.6H2O, Co(NO3)2.6H2O, NiCl2.6H2O, Ni(NO3)2.6H2O,

CuCl2.2H2O, Cu(NO3)2.6H2O, ZnCl2, Zn(NO3)2.6H2O, FeCl2.6H2O,

Fe(NO3)2.6H2O, MnCl2.6H2O, Mn(NO3)2.6H2O (all Aldrich) were commercially available pure samples.

[3.2] Synthesis of 2,11-dioxo-5,8-dithia-1,12-diaza-cyclotetradecane)M(II) 2+ 2+ 2+ 2+ 2+ 2+ chloride/ nitrate [MLX2] (M=Mn , Fe , Co , Ni , Cu , Zn ; X= Cl or NO3)

A mixture of (2mmol) of o-thiosalcylic acid was placed in a round bottom flask, (1mmol) of dibromoethan in 70 ml. of ethanol solvent was then added. The mixture was left under stirring with gentle heating for about 30 minutes. To the above mixture an ethanolic solution of (1mmol) of 1,2diaminoethane is added followed by the addition of (1mmol) of the desired metal salt. The hole contents were left to react for a total of 7-15 hours. The solid product formed, then washed several times with ethanol and dried.

[3.3] Synthesis of 5,9,12,16-tetraoxo-11-thia-1,4,8,13,17-pentaaza- 2+ 2+ 2+ cyclononadecane)M(II) chloride/nitrate [ML]X2(M=Mn , Fe , Co , 2+ 2+ 2+ Ni , Cu , Zn ; X= Cl or NO3)

(2mmol) of 2-amino benzoic acid in ethanol was placed in a round bottom flask, (1mmol) of diethylenetriamin in 75 ml. of alc. Solvent was then added. The mixture was left under stirring with gentle heating for about 30 minutes. To the above mixture an ethanolic solution of (1mmol) of thiodiglycolic acid is added followed by the addition of (1mmol) of the desired metal salt. The whole contents were left to react for a total of 7-15 hours. The solid product formed was fitted off, washed several times with ethanol and then dried.

[3.4] Synthesis of 10,11;14,15;18,19-tribenzo-1,9-dioxo-2,5,8,12,17- pentaazacyclononadecan)M(II) dichloride/nitrate [MLX]X (M=Mn2+, 2+ 2+ 2+ 2+ 2+ Fe , Co , Ni , Cu , Zn ; X= Cl or NO3)

(2mmol) of 2-amino benzoic acid in ethanol was placed in a round bottom flask, (1mmol) of diethylenetriamin in 75ml. of alcohol was then added. The mixture was left under stirring with gentle heating for about 30 minutes. To the above mixture an ethanolic solution of (1mmol) of phthaldehyde is added followed by the addition of (1mmol) of the desired metal salt. The whole contents were left to react for a total of 7-15 hours. The solid product formed, washed several times with ethanol solvent and then dried.

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[46] Transition Metal Complexes of 13-and 14-Membered N2O2 Macrocycles: Synthesis and Characterization. Omar S.M. Nasman. Transition Met. Chem., 285-288,33,2007. [47] Template Synthesis an characterization of Mn (II),Co (II), and Zn (II)

Complexes of 14-17-Membered N2O2 Macrocycles. Omar S.M. Nasman, S.M. Saadeh, H.A.Aziz, H. El-Hendawi, F. Kodeh J.Natural Science, Alazhar Univ. 31-40,10,2008. [48] Nickel(II), Copper (II) and Zinc (II) Complexesof 14- and 15-Membered

N2O2 Macrocycles: Synthesis and characterization. Omar S.M. Nasman, Salman.M. Saadeh, Hassan.A.Aziz, Hussein El- Hendawi, Fawzi Kodeh. J.Appl-Chem,Research., 45-60,7,2008

[49] N2S2-Donor Macrocycles with some Transition Metal Ions: Synthesis and characterization. Omar S.M.Nasman Phosphorus Sulfur and Silicon, 1541-1551,183,2008.

[50] Synthesis and Spectral Studies of 15-and16-Membered Diamide Diimine Tetraaza Macrocyclic Metal Complexes. Omar S.M. Nasman Asian J. Chem., 1231-1238,19,2007. [51] Ligand Design and Metal-ion Recognition: Comparison between the

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بسم اهلل الرحمن الرحيم NEW MACROCYCLES COMPLEXES OF SOME TRANSITION METALS SYNTHESIS AND CHARACTERIZATION

1,2- thiosalysilic acid 1,2-diaminoethane dibromoethane 14- transition metal ions membered dithiadiazamacrocyclic complexes

(2-amino benzoic acid) (thiodiglycolic acid) (diehylenetriamine) transition metal ions 20-membered of thiapentaazamacrocyclic complexes

(2-aminobenzoic acid) (phthaldehyde) (diethylenetriamine) 19- transition metal ions membered of pentaazamacrocyclic complexes