Department of Chemistry

Faculty of Education

Ain Shams University

Synthesis and characteristic studies of metal

complexes of some Schiff bases derived from

o-acetoacetylphenol

A Thesis Submitted by

Mohammed Ali Naji Hassan Mahdi Master of the Teacher’s Preparation in Science (Inorganic Chemistry) 2012

For Ph.D. degree of the Teacher’s Preparation in Science

(Inorganic Chemistry)

Under Supervision

Prof. Dr. Saied Mohamed Khalil

Prof. Dr. Ali Mahmoud Taha

Prof. Dr. Magdy Shebl Saleh El-Sayed

Ass. Prof. Dr. Omima Mohamed Ibrahim Adly

Dr. Hoda Fathy El-Shafiy

Cairo – Egypt

2017

Ain Shams University

Faculty of Education

Title Sheet

Title: Synthesis and characteristic studies of metal complexes of some Schiff bases

derived from o-acetoacetylphenol

Candidate: Mohammed Ali Naji Hassan Mahdi

Degree: Ph.D. degree of the Teacher’s Preparation in Science (Inorganic Chemistry).

Department: Chemistry.

Faculty: Faculty of Education.

University: Ain Shams University.

Date of Award: / / 2017

Approval Sheet

Title: Synthesis and characteristic studies of metal complexes of some Schiff bases

derived from o-acetoacetylphenol

Candidate: Mohammed Ali Naji Hassan Mahdi

Degree: Ph.D. degree of the Teacher’s Preparation in Science (Inorganic Chemistry).

Board of Advisors

Approved by

1) Prof. Dr. Saied Mohamed Khalil

Professor of Inorganic Chemistry, Faculty of Education, Ain Shams University.

2) Prof. Dr. Ali Mahmoud Taha

Professor of Inorganic Chemistry, Faculty of Education, Ain Shams University.

3) Prof. Dr. Magdy Shebl Saleh El-Sayed

Professor of Inorganic Chemistry, Faculty of Education, Ain Shams University.

4) Ass. Prof. Dr. Omima Mohamed Ibrahim Adly

Assist. Professor of Inorganic Chemistry, Faculty of Education, Ain Shams University.

5) Dr. Hoda Fathy El-Shafiy

Lecturer of Inorganic Chemistry, Faculty of Education, Ain Shams University.

Date of presentation: / /2017

Post Graduate Studies

Stamp of Approval / / 2017

Date of Approval: / / 2017

Approval of Faculty Council / / 2017

Approval of University Council / / 2017

Dedication

To

My Family

Acknowledgement

First and foremost, I must acknowledge my limitless thanks to ALLAH,

for His helps and bless. I am totally sure that this work would have never

become truth, without His guidance.

I wish to express my sincere gratitude to Prof. Dr. Saied Mohamed.

Khalil (Professor of Inorganic Chemistry, Faculty of Education, Ain

Shams University and the Faculty's Dean), Prof. Dr. Ali Mahmoud

Taha (Professor of Inorganic Chemistry, Previous Head of the

Chemistry Department Faculty of Education, Ain Shams University),

Prof. Dr. Magdy Shebl Saleh El-Sayed (Professor of Inorganic

Chemistry, Faculty of Education, Ain Shams University), Dr. Omima

Mohamed Ibrahim Adly (Assist. Professor of Inorganic Chemistry,

Faculty of Education, Ain Shams University) and Dr. Hoda Fathy El-

Shafiy (Lecturer of Inorganic Chemistry, Faculty of Education, Ain

Shams University) for their supervision and their continuous guidance

during preparation and valuable discussion throughout this thesis.

Special thanks for Prof. Dr. Mahmoud Mashaly, Head of the

Chemistry Department, Faculty of Education, Ain Shams University,

Prof. Dr. Ali Mahmoud Taha, Previous Head of the Chemistry

Department, Prof. Dr. Mostafa Ismail, Former Head of the Chemistry

Department Faculty of Education, Ain Shams University and Dr. Omima

Mohamed Ibrahim Adly (Assist. Professor of Inorganic Chemistry,

Faculty of Education, Ain Shams University, for their valuable help

making this thesis possible in the present form.

Finally, I would like to thank all staff members and collaborates

of Chemistry Department, Faculty of Education, Ain Shams University

for all their help and encouragement.

Published work

Magdy Shebl, Omima M.I. Adly, Hoda F. El-Shafiy,

Saied M.E. Khalil, A. Taha, Mohammed A.N. Mahdi;

J. Mol. Struct., 1134 (2017) 649-660.

Omima M.I. Adly, Magdy Shebl, Hoda F. El-Shafiy, Saied M.E. Khalil, A. Taha, Mohammed A.N. Mahdi;

J. Mol. Struct., Accepted xxxx(2017) xxxx

Contents

List of Abbreviations i

List of Figures iii

List of Tables x

List of Schemes xii

Preface xiv

Abstract xvi

Aim of the work xvii

Chapter 1

Literature survey

1 Introduction 1

1.1 Literature survey on complexes of Schiff bases derived from

o-acetoacetylphenol

2

1.2 Literature survey on salicylaldehydehydrazone (salH)

complexes

13

1.3 Literature survey on 2-hydroxybenzohydrazone (2-HBH)

complexes

16

1.4 Literature survey on benzoylhydrazone (BH) complexes 21

Chapter 2

Experimental & theoretical background

2.1 Experimental 28

2.1.1 Chemicals and reagents 28

2.1.2 Synthesis of organic ligands 28

2.1.3 Synthesis of metal complexes 35

2.1.4 Analytical determinations and characterizations 37

2.1.5 Quantitative analyses of the metal cations 39

2.1.6 Antimicrobial activity 41

2.1.7 Antitumor activity 43

2.2 Theoretical background of molecular modeling 45

2.2.1 Molecular mechanics 45

2.2.2 Molecular dynamics 46

2.2.3 Quantum mechanics 46

2.2.5 Molecular orbital (MO) theory 47

2.2.5.1 Ab initio calculations 47

2.2.5.2 Semiempirical calculations 48

2.2.5.3 Chemical accuracy 48

2.2.10 Basic concepts 51

2.2.11 Basis sets 52

Results and discussion

Chapter 3

3.1 Abstract 55

3.2 Results and discussion 56

3.2.1 The ligand 56

3.2.2 Metal complexes 59

3.2.2.1 IR spectra of the metal complexes 61

3.2.2.2 Conductivity measurements 63

3.2.2.3 Electronic spectra and magnetic moment measurements 64

3.2.2.4 Thermal analysis 66

3.2.2.5 Mass spectra 67

3.3 Molecular orbital calculations 68

3.4 Biological activity 69

Chapter 4

4.1 Abstract 100

4.2 Results and discussion 101

4.2.1 The ligand 101

4.2.2 Metal complexes 103

4.2.2.1 IR spectra of the metal complexes 106

4.2.2.2 Electronic spectra and magnetic moment measurements 108

4.2.2.3 Thermal analysis 111

4.2.2.4 Mass spectra 113

4.2.2.5 1H-NMR spectra 115

4. 3 Molecular orbital calculations 115

4.4 Biological activity 117

Chapter 5

5.1 Abstract 149

5.2 Results and discussion 150

5.2.1 Conductivity 153

5.2.2 Spectroscopic studies 153

5.2.2.1 Infrared spectra 153

5.2.2.2 1H-NMR spectra 155

5.2.2.3 Electronic spectra and magnetic moment measurements 156

5.2.2.4 Thermal analysis 158

5.3 Antimicrobial activity 160

5.4 Molecular orbital calculations 161

Chapter 6

6.1 Abstract 195

6.2 The aim of this chapter 195

6.3 Results and discussion 196

6.3.1 IR spectra 196

6.3.2 Electronic spectra and conductivity measurements 197

6.3.3 1H NMR spectra 199

6.3.4 Thermal analysis 199

6.3.5 Mass spectra 203

6.4. Molecular Orbital Calculations 206

6.5 Antimicrobial activity 209

Summary 235

References 250

i List of Abbreviations

List of abbreviations

o-AAPh o-Acetoacetylphenol.

salH Salicylaldehyde hydrazone

2-HBH 2-Hyroxybenzohydrazide

BH Benzoyl hydrazone

H3L1 3-[(2-hydroxy-benzylidene)-hydrazono]-1-(2-

Hydroxyphenyl)-butan-1-one

H3L2

(E)-2-hydroxy-N'-(4-(2-hydroxyphenyl)-4-oxobutan-2-

Ylidene)benzohydrazide

H3L3

(E)-N'-(4-(2-hydroxyphenyl)-4-oxobutan-2-

Ylidene)benzohydrazide

1,2-pn 1,2-Diaminopropane

H3La (E)-3-(1-((E)-2-hydroxy-5-nitrobenzylideneamino)

Propan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one

H3Lb (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-

2-ylideneamino) propylimino)indolin-2-one

1,10-phen 1,10-Phenanthroline

8-Hq 8-Hydroxyquinoline

en Ethylenediamine

Sal Salicylaldehyde

nph Naphthaldehyde

DMF Dimethylformamide

Hapash Acetone p-amino acetophenone salicyloyl hydrazone

RSH Resacetophenone salicyloyl hydrazone

TGA Thermal gravimetric analysis

DTA Differential thermal analysis

Py-2-cd Pyridine-2-carbaldehyde

ii List of Abbreviations

Py-2-cdH Pyridine-2-carbaldehyde hydrazone

2-apyH 2-Acetylpyridine hydrazone

MLCT Metal to ligand charge transfer

BH Benzoylhydrazine

py Byridine

NicoH Nicotinoylhydrazine

IPBH Isopropylenebenzoylhydrazine

IP2-HBH Isopropylene 2-hydroxybenzoylhydrazine

IPNH Isopropylenenicotinoylhydrazine

DMSO Dimethylsulphoxide

LNT Liquid nitrogen temperature

DFT Density functional theory

DNA Deoxyribo nucleic acid

LOI Limiting oxygen index

MBH o-Methoxybenzaldehyde benzoylhydrazone

EDTA-Na2 Ehylenediaminetetraacetic acid disodium salt dihydrate

MO Molecular orbital

ΔHf Heat of formation

HOMO High occupied molecular orbital

LUMO Low unoccupied molecular orbital

LCAO-MO

ZINDO

GTOS

Linear combination of atomic orbitals - molecular orbital

Zerners intermediate neglect of differential overlap

Gaussian type orbitals

iii List of

Abbreviations

iii List of Figures

List of Figures

No. Figures Page

1.1 The proposed structures of the mono-nuclear complexes

of ligand, 5-methyl-3-(2-hydroxyphenyl)pyrazole

2

1.2. Suggested structures of mono- and bi-nuclear metal

complexes of the ligand, 3-(2-iminoethane)-1-(o-hydroxy

-phenyl)-1-butanone (H2L).

4

1.3. Mono-, bi- and tri-nuclear metal complexes of

salicylaldimine

5

1.4. Suggested structures of mononuclear VO(IV), Fe(III)

Ni(II), Co(II) and Cu(II) complexes of ligand, H3La

6

1.5. The structures of binuclear Co(II), Ni(II), Cu(II), and

UO2(VI) complexes of ligand, H3Lb

6

1.6a. Proposed structures of the mixed thiocyanate

oxorhenium(V) complexes

7

1.6b. Proposed structures of the mixed 1,10-phenanthroline

oxorhenium(V) complexes

7

1.7. Structures of heteronuclear complexes of oxorhenium(V)

and Fe(III) ions

8

1.8a. Proposed structures of the mononuclear complex (A) and

heteronuclear complex (B)

9

1.8b. Proposed structures of the heteronuclear of the complexes 9

1.9. Mono- and bi-nuclear Ni(II) complexes 10

1.10. Proposed structures of the Cu(II), Ni(II) and VO(IV)

complexes

11

1.11a. Proposed structures of mono- and bi-nuclear VO(IV) and

UO2(VI) complexes

12

1.11b. The molecular structure of VO(H2aapen) complex 12

1.12. Suggested structures for mono- and bi-nuclear complexes. 13

1.13a. Structure of salicylaldehyde acyldihydrazones H4Ln 13

1.13b Structure of the monomeric [Cu2(H2L1)(H2O)2]

2+ cation 14

1.14. Representative structures of the Mn(II), Ni(II), Co(II),

Cu(II) and Zn(II) complexes

16

1.15. Proposed structures of Fe(II) and Fe(III) complexes 17