DOCSLIB.ORG

Thesis Style Document

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Thesis Style Document Studies Towards the Asymmetric Synthesis of Cyclochiral Rotaxanes and Au(III)-oxo Complexes as Catalysts James Alan Thomas O’Neill Submitted for the degree of Doctor of Philosophy Heriot-Watt University School of Engineering and Physical Sciences April 2015 The copyright in this thesis is owned by the author. Any quotation from the thesis or use of any of the information contained in it must acknowledge this thesis as the source of the quotation or information. ABSTRACT The work reported in this thesis consists of studies towards the asymmetric synthesis of mechanically planar chiral rotaxanes via desymmetrisation approach. It describes the synthesis of a novel macrocycle and the investigation of this macrocycle as a potential ligand in the Cadiot-Chodkiewicz and CuAAC ‘click’ reactions as part of the study towards the synthesis of asymmetric planar chiral rotaxanes. Furthermore, the use of Au(III)-oxo complexes as potential catalysts in a model hydroamination reaction are described. The thesis is divided into four chapters: Chapter one is an introduction to rotaxanes and includes an overview of the synthesis of rotaxanes and chirality in rotaxanes. Chapter two is an account of the synthesis of a novel macrocycle and details attempts to implement this macrocycle towards the synthesis of a rotaxane using the Cadiot- Chodkiewicz and CuAAC ‘click’ reactions. Chapter three describes optimisation and multi-gram scale-up of the synthetic route towards a novel C1-symmetric bis(oxazoline) macrocycle first synthesised in our group by Pauline Glen. Chapter four describes our investigation into the use of Au(III)-oxo complexes for use as catalysts in a model hydroamination reaction. i DEDICATION I would like to dedicate this work to my wife, Andrea. ii ACKNOWLEDGEMENTS First and foremost, I would like to thank Ai-Lan for the opportunity to work in the Lee group on what has been a challenging project and for all the support, advice and endless patience you have given me throughout my studies and the writing process. Thanks to Pauline, Paul, Jamie, Sarah, Mari and Robert who have all provided support, guidance and continued friendship. I would like to thank all the staff in the chemistry department at Heriot-Watt for the expertise they have passed on and for all the support throughout all the years I have been here. In particular, thank you to the members of the organic chemistry section who have provided invaluable help throughout this project and to Alan Boyd and Georgina Rosair for their guidance around NMR and Single Crystal X-Ray Diffraction. Special thanks also go to Christina Graham for all her help throughout my time at Heriot-Watt. Thanks go to the EPSRC for providing the funding for this project. Last, but not least, a big thank you to my family. Andrea, thank you for your love, support and encouragement throughout this work. Without it, I wouldn’t have got there. To my Mum and Dad, thank you for always pushing me to achieve the best I can in life. I will always be grateful for your sacrifices over the years. iii ACADEMIC REGISTRY Research Thesis Submission Name: James Alan Thomas O’Neill School/PGI: School of Engineering and Physical Sciences Version: (i.e. First, Final Degree Sought Doctor of Philosophy Resubmission, Final) (Award and Chemistry Subject area) Declaration In accordance with the appropriate regulations I hereby submit my thesis and I declare that: 1) the thesis embodies the results of my own work and has been composed by myself 2) where appropriate, I have made acknowledgement of the work of others and have made reference to work carried out in collaboration with other persons 3) the thesis is the correct version of the thesis for submission and is the same version as any electronic versions submitted*. 4) my thesis for the award referred to, deposited in the Heriot-Watt University Library, should be made available for loan or photocopying and be available via the Institutional Repository, subject to such conditions as the Librarian may require 5) I understand that as a student of the University I am required to abide by the Regulations of the University and to conform to its discipline. * Please note that it is the responsibility of the candidate to ensure that the correct version of the thesis is submitted. Signature of Date: Candidate: Submission Submitted By (name in capitals): ANDREA MCVITTIE Signature of Individual Submitting: Date Submitted: For Completion in the Student Service Centre (SSC) Received in the SSC by (name in capitals): Method of Submission (Handed in to SSC; posted through internal/external mail): E-thesis Submitted (mandatory for final theses) Signature: Date: iv TABLE OF CONTENTS ABSTRACT ..................................................................................................................... I DEDICATION ................................................................................................................ II ACKNOWLEDGEMENTS ......................................................................................... III TABLE OF CONTENTS ............................................................................................... V ABBREVIATIONS ..................................................................................................... VII CHAPTER 1 – INTRODUCTION ................................................................................ 1 1.1 Mechanically Interlocked Molecular Architectures ........................................... 1 1.2 Nomenclature of Rotaxanes ............................................................................... 1 1.3 Applications of Molecular Interlocked Architectures ........................................ 2 1.4 Overview of Classical Synthetic Methodologies of Rotaxanes ......................... 6 1.4.1 Early Statistical Approaches ....................................................................... 7 1.4.2 Directed Synthesis by Covalent Bond Formation ....................................... 7 1.4.3 Cyclodextrin Mediated Template Synthesis ............................................... 8 1.4.4 Hydrogen Bond Mediated Templating........................................................ 9 1.4.5 π-electron donor/π-electron acceptor interactions ..................................... 12 1.4.6 Transition Metal Templating .................................................................... 13 1.5 Active Metal Template Synthesis of Rotaxanes ............................................... 14 1.5.1 CuAAc Active Metal Template For Rotaxane Synthesis ......................... 16 1.5.2 Copper Mediated Oxidative Alkyne-Alkyne Homocoupling ................... 17 1.5.3 Copper Mediated Alkyne-Alkyne Heterocoupling ................................... 19 1.5.4 Palladium(II)-Catalysed Active Metal Template Reactions ..................... 20 1.6 Cyclochirality and Rotaxanes ........................................................................... 23 CHAPTER 2 – STUDIES TOWARDS THE SYNTHESIS OF A CYCLOCHIRAL ROTAXANE .................................................................................................................. 25 2.1 Results and Discussion ..................................................................................... 25 2.1.1 Project Overview ....................................................................................... 25 2.1.2 Design of a Prochiral Rotaxane for Desymmetrisation............................. 25 2.1.3 Synthetic overview of the target prochiral rotaxane ................................. 26 2.2 Preparation of Macrocycle 2.1 ......................................................................... 27 2.3 Synthesis of Macrocycle Precursor 2.22 .......................................................... 30 2.4 Preparation of Macrocycle 2.26 ....................................................................... 35 2.5 Synthesis of Macrocycle Precursor 2.27 .......................................................... 36 2.6 Synthesis of Macrocycle Precursor 2.28 .......................................................... 40 2.7 Preparation of Macrocycle Precursor 2.43 ....................................................... 43 2.8 Synthesis of Macrocycle 2.42 .......................................................................... 45 2.9 Cadiot-Chodkiewicz Heterocoupling Reaction ................................................ 46 2.9.1 Introduction ............................................................................................... 46 2.9.2 Cadiot-Chodkiewicz in Supramolecular Chemistry.................................. 47 2.9.3 Synthesis of Stoppers for the Cadiot-Chodkiewiz Reaction ..................... 48 2.10 Cadiot-Chodkiewicz Reaction Results ............................................................. 49 2.11 Conclusion ........................................................................................................ 50 v 2.12 CuAAC ‘Click’ Reaction ................................................................................. 52 2.12.1 Introduction ............................................................................................... 52 2.12.2 CuAAC ‘Click’ Reaction in Supramolecular Chemistry .......................... 52 2.12.3 Investigation of the use of the CuAAC ‘Click’ Reaction for Rotaxane Formation ................................................................................................................. 52 2.12.4 Synthesis of Suitable Rotaxane Stoppers for a CuAAC ‘click’ Reaction . 53 2.13 CuAAC Reaction Results ................................................................................
Load more

Recommended publications
  • Mie University Department of Chemistry for Materials
    Mie University Department of Chemistry for Materials General Principles and Selected Examples in Supramolecular Chemistry Prof. Yang Kim (ykim@kumamoto-u.ac.jp) Kumamoto University 2. Solution host-guest chemistry 2.1 Introduction: guests in solution The host–guest chemistry of anions, cations and neutral-guest species in solution. The electrostatic charge on any ion must be balanced by a corresponding counter-ion. Thus a ‘cation’ or ‘anion’ host is always a host for an ion pair (either contact or solvent-separated). The effect of the counter-ion is sometimes ignored or assumed to be negligible, particularly + - − if weakly interacting counter-ions are used, such as NBu 4 , PF 6 , or B(C 6H3(CF 3)2)4 . However, there are a number of successful ion-pair binding hosts . Macrocyclic receptor that binds solvent separated ion-pairs Association of ZnDPA probe with phosphatidylserine head group. False colored fluorescence image of a living rat bearing two tumors. 2.2 Macrocyclic versus acyclic hosts Two major classes of host: acyclic (podands ) and cyclic (macrocycles, macrobicycles or macrotricycles ). Podand : An acyclic chain-like or branching host with a number of binding sites that are situated at intervals along the length of the molecule, or about a common spacer. Podand: Linear or branching chain species with two or more sets of guest-binding functional groups positioned on the spacer unit in such a way as to chelate a target guest species to maximise guest affinity (cf . co-operativity ). Podands generally have a high degree of flexibility and on binding to a guest the conformational change that occurs to produce a stable host–guest complex, may result in allosteric effects .
    [Show full text]
  • Study the Important Characteristics of the Macrocyclic Complexes
    INTERNATIONAL JOURNAL OF RESEARCH CULTURE SOCIETY ISSN: 2456-6683 Volume - 1, Issue - 08, Oct – 2017 UGC Approved Monthly, Peer-Reviewed, Refereed, Indexed Journal Publication Date: 30/10/2017 STUDY THE IMPORTANT CHARACTERISTICS OF THE MACROCYCLIC COMPLEXES Sneha Thahiya1 Dr.Dheeraj Kumar2 1 Research scholar Singhania university Rajasthan 2 Assistant professor government college Narnaul Haryana Email - dheerajyadav30@gmail.com Abstract: The metal-ion and host-guest chemistry of macro cyclic ligands have developed rapidly over recent years and now impinge on wide areas of both chemistry and biochemistry. Macro cyclic ligands are polydentate ligands containing their donor atoms either incorporated in or, less commonly, attached to a cyclic back bone. A large number of synthetic, as well as many natural, macro cycles 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 investigations of spectral, electrochemical, structural, kinetic and thermodynamic aspects of macro cyclic complex formation have all received considerable attention. Key Words: Macro cyclic ligands, Cyclic ligand complexes, host-guest Addition etc. 1. INTRODUCTION : The development of the field of bioinorganic chemistry has been an important factor in spurring the growth of interest in the macro cyclic complexes. The possibility of using synthetic macro cycle as model for biologically important system has initiated a broad spectrum of research activities, ranging from synthesis of new ring systems and studies on the properties and function of macro cyclic complexes to their application in industry, medicine and other field. The field of macro cyclic chemistry of metals is developing very fast because of its variety of applications and importance in the area of coordination chemistry.
    [Show full text]
  • Novel Metal Template Strategies for the Construction of Rotaxanes and Catenanes
    Novel Metal Template Strategies for the Construction of Rotaxanes and Catenanes Roy T. McBurney Degree of Doctor of Philosophy School of Chemistry The University of Edinburgh December 2008 Dedicated to My Family i Contents Abstract and Layout of Thesis .................................................................................... v Declaration .............................................................................................................. vii Lectures and Meetings Attended and Presentations Given ....................................... viii Acknowledgements .................................................................................................... x General Comments on Experimental Data ................................................................ xii Chapter 1: Recent Advances in the Metal Template Synthesis of Catenanes, Rotaxanes, Knots and Links 1 Synopsis .................................................................................................................... 2 1.1 Ordering and Entwining about a Metal Template ................................................. 3 1.2 “Passive” Metal Template Synthesis of Rotaxanes and Catenanes ........................ 7 1.3 Knots ................................................................................................................. 28 1.4 Borromean Rings ............................................................................................... 33 1.5 “Active” Metal Template Synthesis of Rotaxanes .............................................
    [Show full text]
  • Managing Tight Binding Receptors for New
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he Most Powerful Ligands--An Under Utilized Resource . 6 A Limiting Moleular Lethargy. 7 Exploiting and Overcoming that Molecular Lethargy. 7 METHODS AND RESULTS Principles of Tight-binding by Ligands. 8 Replacing Equilibration with More Rapid Switching Processes . 9 Design and Synthesis of Generation 1 Switch-binding Ligands . 9 Validation of Concept: Studies on In Situ Produced Generation 0 Ligand. 11 Proof of the Template Switch-binding Concept Using Generation 1 Ligand . 13 Generation 2 Ligands-- an Untested Second Example . 18 Switch-release Studies--A replacement for Slow Equilibrium Release . 19 Photorelease of Metal Ions from Tightly Bound Adducts . 19 Slow Separations Methodology--an Extreme Case of Biomimicry . 20 Macroporous Polymers. 21 Polymer Synthesis . .21 Polymer Characterization. 22 RELEVANCE, IMPACT AND TECHNOLOGY TRANSFER Relevance to Critical DOE Environmental Management Problems . 23 Deactivation and Decommissioning.. 24 Environmental Restoration. 24 High-level Waste. 24 MLLW/TRU and Spent Nuclear Fuel. 25 Reducing Costs, Schedules and Risks and Improved Compliance. 25 Bridging the Gap between Basic Research and Timely Needs-Driven Applications. 25 Impact on possible Users and the Identification of Those Users . 26 Are Larger Scale Trials Warranted?.
    [Show full text]
  • NMR Studies of Inclusion Compounds
    NMR Studies of Inclusion Compounds Sahar Nikkhou Aski Stockholm University © Sahar Nikkhou Aski, Stockholm 2008 ISBN 978-91-7155-715-5 Printed in Sweden by US-AB, Stockholm 2008 Distributor: Department of Physical, Inorganic and Structural Chemistry Stockholm University ii NMR Studies of Inclusion Compounds Sahar Nikkhou Aski Abstract This thesis presents the application of some of the NMR methods in studying host- guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self- diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information, give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari- Szabo, axially symmetric rigid body, and Clore models.
    [Show full text]
  • Catenanes German Edition: DOI: 10.1002/Ange.201411619 Catenanes: Fifty Years of Molecular Links GuzmN Gil-RamRez, David A
    Angewandte. Reviews D. A. Leigh et al. International Edition: DOI: 10.1002/anie.201411619 Catenanes German Edition: DOI: 10.1002/ange.201411619 Catenanes: Fifty Years of Molecular Links Guzmn Gil-Ramrez, David A. Leigh,* and Alexander J. Stephens Keywords: catenanes · interlocked molecules · links · supramolecular chemistry · template synthesis Angewandte Chemie 6110 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2015, 54, 6110 – 6151 Ü Ü These are not the final page numbers! Angewandte Catenane Synthesis Chemie Half a century after Schill and Lttringhaus carried out the first From the Contents directed synthesis of a [2]catenane, a plethora of strategies now exist for the construction of molecular Hopf links (singly interlocked rings), 1. Introduction 6111 the simplest type of catenane. The precision and effectiveness with 2. Synthesis of Hopf Link (Singly which suitable templates and/or noncovalent interactions can arrange Interlocked) [2]Catenanes 6116 building blocks has also enabled the synthesis of intricate and often beautiful higher order interlocked systems, including Solomon links, 3. Higher Order Linear and Radial Borromean rings, and a Star of David catenane. This Review outlines [n]Catenanes 6125 the diverse strategies that exist for synthesizing catenanes in the 21st 4. Higher Order Entwined century and examines their emerging applications and the challenges [n]Catenanes 6130 that still exist for the synthesis of more complex topologies. 5. Catenanes as Switches, Rotary Motors, and Sensors 6134 1. Introduction 6. Catenane Linkages Incorporated into Polymer Over the last fifty years, research into the synthesis of Chains, Materials, and interlocked molecules has evolved from a concept viewed Attached to Surfaces 6140 with some scepticism to a reality in which ways to harness the properties afforded by mechanical bonding are now being 7.
    [Show full text]
  • Vronaldson Thesis May09.Pdf (5.506Mb)
    Active Template Strategies for the Assembly of Mechanically Interlocked Molecules Vicki E. Ronaldson Degree of Doctor of Philosophy School of Chemistry University of Edinburgh May 2009 Vicki E. Ronaldson, 2009 2 Vicki E. Ronaldson, 2009 Dedicated to my Family i Vicki E. Ronaldson, 2009 Table of Contents Abstract ...................................................................................................................iv Declaration ............................................................................................................... v Conferences and Meetings Attended ......................................................................vi Acknowledgements...............................................................................................viii List of Abbreviations ............................................................................................viii General Comments on Experimental Data............................................................... x Thesis Layout..........................................................................................................xi Chapter 1: Introduction to the Templated Assembly of Mechanically Interlocked Molecules................................................................................................ 1 1.1 Mechanical Bonds and Interlocked Molecules ............................................ 2 1.2 Histrory and Early Synthetic Attempts ........................................................ 3 1.3 Template-Directed Synthesis ......................................................................
    [Show full text]
  • A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry
    SYNTHESIS AND CHARACTERIZATION OF APPROPRIATE MACROCYCLIC COMPLEXES OF NICKEL (II) METAL ION A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry SUBMITTED BY MD. SHAHEDUR RAHMAN ROLL NO. 1014032704 F SESSION: OCTOBER-2014 DEPARTMENT OF CHEMISTRY BANGLADESH UNIVERSITY OF ENGINEERING & TECHNOLOGY (BUET) DHAKA-1000, BANGLADESH MARCH-2017 STATEMENT OF THE AUTHOR By my signature below, I declare and affirm that this thesis is my own work. I have followed all ethical principles of scholarship in the preparation, data collection, data analysis and completion of this thesis. All scholarly matter that is included in the thesis has been given recognition through citation. I verify that I have cited and referenced all sources used in this document. Every serious effort has been made to avoid any plagiarism in the preparation of this thesis. ………………………………………… Md. Shahedur Rahman (Candidate) M. Sc. student Roll No-1014032704F Department of Chemistry BUET, Dhaka Bangladesh DEDICATED To my parents, who sacrificed every personal comfort to see me through my basic education ACKNOWLEDGMENTS I am very much grateful to the Almighty Allah for enabling me to complete this work. I would like to acknowledge my sincere thanks to my supervisor, Prof. Dr. Md. Rafique Ullah for his invaluable help, thought-provoking guidance, encouraging attitude and pleasant behavior throughout this study. I also feel a great pleasure to convey profound veneration and deep appreciation to my respected teachers, Professor Dr. Md. Nazrul Islam, Professor Dr. Shakila Rahman and all other teachers of the Department of Chemistry, BUET for their cordial co-operation and guidance specially for providing laboratory facilities to carry out my research.
    [Show full text]
  • Synthetic Approaches to Lanthanide Complexes with Tetrapyrrole Type Ligands
    Russian Chemical Reviews 77 (10) 875 ± 907 (2008) # 2008 Russian Academy of Sciences and Turpion Ltd DOI 10.1070/RC2008v077n10ABEH003879 Synthetic approaches to lanthanide complexes with tetrapyrrole type ligands V E Pushkarev, L G Tomilova, Yu V Tomilov Contents I. Introduction 875 II. Synthesis of single-decker complexes 876 III. Synthesis of homoleptic double-decker complexes 879 IV. Synthesis of homoleptic triple-decker complexes 885 V. Synthesis of heteroleptic and mixed-ligand double-decker complexes 888 VI. Synthesis of heteroleptic and mixed-ligand triple-decker complexes 896 Abstract. Approaches to the synthesis of single-, double- linear optics.3 The prospects for preparing heteroleptic, and triple-decker complexes of lanthanides with phthalo- mixed-ligand or heterometallic sandwich complexes based cyanines and their analogues known to date are considered. on phthalocyanines 4, 5 create grounds for the development Examples of preparation of sandwich-type complexes based of materials with specified properties.6, 7 Thus, studies of on other metals of the Periodic System are given. The phthalocyanine derivatives of lanthanides are important bibliography includes 222 references.references. from both the fundamental and applied standpoints. Of particular significance is the development of efficient and I. Introduction selective methods for the synthesis of complexes of a required structure. In recent decades, complexes of phthalocyanines and their The synthesis of lanthanide phthalocyanines is based on analogues with various metals have been the subject of either template tetramerisation of phthalonitriles with lan- vigorous research. Owing to their structural features, in thanide salts or direct reaction of the salts with free particular, multiple-circuit aromatic conjugation system, phthalocyanine ligands.4, 5, 8 ± 13 The recent progress in the these compounds possess unique physicochemical proper- latter method stimulated the search for optimal approaches ties.
    [Show full text]
  • SYNTHESIS and INVESTIGATION of STABILITY and CHEMICAL KINETICS of CROWN ETHERS and THEIR COMPLEXES with 3D TRANSITION METALS
    SYNTHESIS AND INVESTIGATION OF STABILITY AND CHEMICAL KINETICS OF CROWN ETHERS AND THEIR COMPLEXES WITH 3d TRANSITION METALS Submitted By IMDAD HUSSAIN 2008-Ph.D-Chemistry-03 Supervisor Prof. Dr. Syeda Rubina Gilani DEPARTMENT OF CHEMISTRY University of Engineering & Technology, Lahore-Pakistan (2015) i Synthesis and Investigation of Stability and Chemical Kinetics of Crown Ethers and Their Complexes With 3d Transition Metals IMDAD HUSSAIN (2008- Ph.D Chemistry-03) Department of Chemistry University of Engineering and Technology, Lahore Supervisor: Dr. Syeda Rubina Gilani A dissertation submitted to University of Engineering & Technology Lahore in accordance with requirements of the degree of Ph. D in Faculty of Science. (2015) ii Synthesis and Investigation of Stability and Chemical Kinetics of Crown Ethers and Their Complexes With 3d Transition Metals This Research Thesis Is Submitted To the Department Of Chemistry, University Of Engineering & Technology Lahore for the Fulfillments for the Degree of DOCTOR OF PHILOSOPHY In CHEMISTRY Approved on ________________ Internal Examiner: Signature: _______________________ (Supervisor) Name: Prof. Dr. Syeda Rubina Gilani External Examiner: Signature: ________________________ Name: ___________________________ Chairperson of the Department: Signature: ______________________ Name: Prof. Dr. Syeda Rubina Gilani DEPARTMENT OF CHEMISTRY UNIVERSITY OF ENGINEERING & TECHNOLOGY LAHORE iii FORM FOR THE RELEASE OF RESEARCH THESIS FOR EXAMINATION Declaration by the Candidate I, IMDAD HUSSAIN, declare that the thesis titled “Synthesis and Investigation of Stability and Chemical Kinetics of Crown Ethers and Their Complexes With 3d Transition Metals” is my own work and has not been submitted previously in whole or in part in respect of any other academic award. ____________________ _________________ Signature of Candidate Date I approved that the above thesis can be submitted for examination.
    [Show full text]
  • Re(CO)3 TEMPLATE FORMATION of DIIMINOISOINDOLINE BASED CHELATES a Dissertation Presented to the Graduate Faculty at the Univers
    Re(CO)3 TEMPLATE FORMATION OF DIIMINOISOINDOLINE BASED CHELATES A Dissertation Presented to The Graduate Faculty at The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Allen Jordan Osinski May 2018 Re(CO)3 TEMPLATE FORMATION OF DIIMINOISOINDOLINE BASED CHELATES Allen Jordan Osinski Dissertation Approved: Accepted: ___________________________ ___________________________ Advisor Department Chair Dr. Christopher J. Ziegler Dr. Christopher J. Ziegler ___________________________ ___________________________ Committee Member Dean of the College Dr. Claire A. Tessier Dr. John C. Green ___________________________ ___________________________ Committee Member Dean of the Graduate School Dr. Wiley J. Youngs Dr. Chand K. Midha ___________________________ ___________________________ Committee Member Date Dr. Yi Pang ___________________________ Committee Member Dr. Chrys Wesdemiotis ii ABSTRACT Over the last century, in the field of coordination chemistry, the number of template reactions has expanded into a diverse collection which can produce a variety of compounds. These template reactions have been used to afford compounds that would be difficult to obtain otherwise. One of the most famous template reactions is the synthesis of phthalocyanine, which was investigated by Linstead. After exploring the chemistry of phthalocyanine, Linstead synthesized hemiporphyrazines and bis(2- iminopyridyl)isoindolines from 1,3-diiminoisoindoline and various primary amines. Later, Siegl improved the synthesis of the hemiporphyrazines and the bis(2- iminopyridyl)isoindolines by employing a calcium ion as a templating agent. The template formation of isoindoline based macrocyclic compounds has been explored, however, the template formation of isoindoline based chelates is relatively unexplored. Due to its restrictive facial arrangement of carbonyl ligands and propensity to coordinate nitrogenous bases, the Re(CO)3-unit is a prime candidate for templating the formation of isoindoline based chelates.
    [Show full text]
  • 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.
    [Show full text]