Coordination chemistry of barbituric acid, its diethyl derivative and benzildiimine with transition metals [Elektronische Ressource] / Nadera Haque

Nadera Haque

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2009
• Nombre de lectures: 37
• Langue: Deutsch
• Poids de l'ouvrage: 8 Mo

Extrait

 
Dissertation zur Erlangung des Doktorgrades 
der Fakultät für Chemie und Pharmazie 
der Ludwig‐Maximilians‐Universität München 
 
 
COORDINATION CHEMISTRY OF BARBITURIC ACID, 
ITS DIETHYL DERIVATIVE AND BENZILDIIMINE WITH 
TRANSITION METALS 
 
 
 
 
NADERA HAQUE 
aus 
Dhaka (Bangladesch) 
 
 
2009 
Erklärung

Diese Dissertation wurde im Sinne von § 13 Abs. 3 der Promotionsordnung vom 29. Januar
1998 von Herrn Prof. Dr. Ingo-Peter Lorenz betreut.




Ehrenwörtliche Versicherung

Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet.




München, am 02.07.2009




Nadera Haque






Dissertation eingereicht am 02.07.2009
1. Gutachter: Prof. Dr. I.-P. Lorenz
2. Gutachter: Prof. Dr. W. Beck
Mündliche Prüfung am 09.10.2009
















TO
MY FAMILY













Die vorliegende Arbeit wurde in der Zeit von Januar 2006 bis März 2009 am
Department für Chemie und Biochemie der Ludwig-Maximilians-Universität München
unter Anleitung von


Prof. Dr. Ingo-Peter Lorenz


angefertigt.
























Acknowledments 

First of all I would like to express my sincere gratitude to my advisor Prof. Dr. Ingo-Peter
Lorenz, for giving me the opportunity to work in his research group and to have flourished
under his guidance. Your insight, knowledge, persistence, patience, dedication, inspiration
and support have helped me more than you know these past three years. Thank you for
always being there to answer my questions, inspiring me to take my science to a new level.

Many thanks that I cannot say enough, to Prof. Dr. W. Beck for the evaluation of the thesis.

My heart-felt gratitude goes to Mrs. Hermione Mayer, Mrs. Gabriele Schmeißer, for their
official supports regarding the paper work, nice conversation and friendly behaviour. I thank
to Mrs. Schmeißer from the deep of my heart for arranging the room, faxing, printing and
helping me for the publications. Without your help I would be homeless in the crucial stage
of my research work.

I will be forever grateful to Mrs. Edith Karaghiosoff not only for helping me in different
experimental works but also making me feel like I am at home. Whenever I had difficulties
in my work or shifting home and many more you were always there for me. I will miss our
enjoyable lunch time conversation which helped me lot to know many unknown things of
Germany.

To my former research lab mates Dr. Bernd Neumann, Dr. Roman Bobka and Atilla Nal,
thank you for the helpful discussions, guidance and the introduction to different techniques
when I first joined the group. Special thanks go to Bernd for solving the molecular structures
within unbelievably short time without any hesitation and to Roman for always inviting me
in the social events of the group.

Brigitte Köhler and Susanne Kammerer, thank you for all of your support (specially for the
publications), knowledge, laughs, helpful discussions, arrangement of nice birthday gifts and
many cheerful memories we have shared. In particular, I thank Brigitte, for her help
numerous times regarding various softwares, CIF files etc.
Thanks to Dr. Nicolas Rödel for solving the molecular structures and Stefan Wirth for
providing the softwares and solving computer problems.

I am grateful to P. Mayer, C. Neumann, Prof. Dr. K. Karaghiosoff (NMR spectroscopy), Dr.
G. Fischer, D. Ewald, Dr. W. Spahl, A. Andres (mass spectroscopy), G. Käser and R. Eicher
(elemental analysis), S. Albrecht and Dr. Mayer (X-ray crystallography) for their work in the
analytical services. Special thanks to Prof. Karaghiosoff for the interpretation of the NMR
spectra and Dr. Mayer for solving some structures.

Prof. Dr. A. Kornath and his co-workers, thanks for the enjoyable atmosphere in the kitchen
and for the arrangement of nice summer parties and excursions.

I also thank to Prof. Dr. T. M. Klapötke for allowing me to attend his lectures and for the
kind permission to use the IR spectrometer.

I wish to express my sincere gratitude to the Bayerische Forschungsstiftung München for
arranging the scholarship and to Ludwig-Maximilians-University for the support of my
research in this renowned university.

I would like to greatly thank my parents, Fazlul Haque and Hasina Haque, for always being
there and believing in me, supporting my every decision, encouraging me to be my best and
loving me. Without your hard work I would not be where I am today. Thanks, to my two
brothers for their help.

Finally, I thank my husband Delwar for providing me an endless source of support and
encouragement throughout my work.









TABLE OF CONTENTS 
 
List of Figures…………………………………………………………………………........v
List of Schemes …………………………………………………………………………....vii
List of Abbreviations……………………………………………………………………...viii

1 Introduction ................................................................................................... 1
1.1 History and importance of Barbituric acid derivatives.................................... 1
1.1.1 Synthesis and characteristic of barbiturates..................................................... 2
1.1.2 The coordination chemistry of barbiturates..................................................... 6
1.1.3 Applications of metal complexes of biologically active ligands..................... 9
1.2 Benzil-bis(trimethylsilyl)diimine.................................................................. 11
1.2.1 Synthesis, properties and coordination chemistry of Si BDI and H BDI ..... 11 2 2
1.3 Aim of the study ............................................................................................ 19

2 Results and discussion................................................................................. 20
2.1 Chromium complexes of barbiturates............................................................ 20
2.1.1 Synthesis of Hdebarb complex of chromium(0)............................................ 20
2.1.2 Molecular structure of 6 ................................................................................ 21
2.1.3 Spectroscopic characterisation of 6 ............................................................... 23
2.2 Synthesis of Hdebarb complex of rhenium(I) ............................................... 25
2.2.1 Molecular structure of 7 26
2.2.2 7 28
2.3 Mono- and di-nuclear rhenium(I) complexes of H debarb ........................... 30 2
2.3.1 Molecular structure of 8 and 9....................................................................... 31
2.3.2 Spectroscopic characterisation of 8 and 9 ..................................................... 34
2.4 Palladium(II) complexes of barbiturates ....................................................... 35
2.4.1 Synthesis of Hbarb complex of palladium(II) ............................................... 36
2.4.1.1 Molecular structure of 10 .......................................................................... 36
2.4.1.2 Spectroscopic characterisation of 10 ......................................................... 38
2.4.2 Synthesis of Hdebarb complex of Pd(II) ....................................................... 39
2.4.2.1 Molecular structure of 11 40
2.4.2.2 11 42
i
2.5 Copper complexes of barbiturates ................................................................. 43
2.5.1 Synthesis of Hdebarb complex of copper(I).................................................. 43
2.5.2 Molecular structure of 12 .............................................................................. 43
2.5.3 Spectroscopic characterisation of 12 ............................................................. 46
2.6 Rhodium complexes of barbiturates.............................................................. 47
2.6.1 Synthesis of Hdebarb complex of rhodium(I) ............................................... 47
2.6.1.1 Molecular structure of 13 .......................................................................... 47
2.6.1.2 Spectroscopic characterisation of 13 ......................................................... 50
2.7 Synthesis of Hdebarb complexes of Rh(II