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Publié par | rheinische_friedrich-wilhelms-universitat_bonn |
Publié le | 01 janvier 2011 |
Nombre de lectures | 51 |
Langue | Deutsch |
Poids de l'ouvrage | 15 Mo |
Extrait
N-Heterocyclic Carbene Palladium Pincer
Complexes: Synthesis, Aggregations and
Catalytic Applications
Dissertation
zur
Erlangung des Doktorgrades (Dr. rer. nat.)
der
Mathematisch-Naturwissenschaftlichen Fakultät
der
Rheinischen Friedrich-Wilhelms-Universität Bonn
vorgelegt von
Jagadeesh Malineni
aus
Hyderabad, Indien
Bonn 2011
N-Heterocyclic Carbene Palladium Pincer
Complexes: Synthesis, Aggregations and
Catalytic Applications
Dissertation
zur
Erlangung des Doktorgrades (Dr. rer. nat.)
der
Mathematisch-Naturwissenschaftlichen Fakultät
der
Rheinischen Friedrich-Wilhelms-Universität Bonn
vorgelegt von
Jagadeesh Malineni
aus
Hyderabad, Indien
Bonn 2011
Die vorliegende Arbeit wurde in der Zeit von January 2008 bis August 2011 unter der Leitung
von Prof. Dr. Karl Heinz Dötz am Kekulé-Institut für Organische Chemie und Biochemie der
Rheinischen Friedrich-Wilhelms-Universität Bonn
Angefertigt und deren Durchführung von der Mathematisch-Naturwissenschaftlichen Fakultät der
Rheinischen Friedrich-Wilhelms-Universität Bonn genehmigt.
Teile dieser Arbeit sind bereits veröffentlicht:
1. “A Novel Pyridine-Bridged Bis-benzimidazolylidene Pincer Palladium Complex:
Synthesis and Catalytic Properties”. Tu Tao, Jagadeesh Malineni, Karl Heinz Dötz, Adv. Synth.
Catal, 2008, 350, 1791-1795.
2. “A Lutidine-Bridged Bis-Perimidinium Salt: Synthesis and Application as a Precursor in
Palladium-Catalyzed Cross-Coupling Reactions”. Tao Tu, Jagadeesh Malineni, Xiaoling Bao
and Karl Heinz Dötz, Adv. Synth. Catal, 2009, 351, 1029-1034.
Members of the examination committee:
1. Prof. Dr. K. H. Dötz
2. Prof. Dr. A. Lützen
3. Prof. Dr. W. Mader
4. Prof. Dr. K. Maier
Tag der Promotion: 20.10.2011
Erscheinungsjahr: 2011
ii
Die vorliegende Arbeit wurde in der Zeit von January 2008 bis August 2011 unter der Leitung
von Prof. Dr. Karl Heinz Dötz am Kekulé-Institut für Organische Chemie und Biochemie der
Rheinischen Friedrich-Wilhelms-Universität Bonn
Angefertigt und deren Durchführung von der Mathematisch-Naturwissenschaftlichen Fakultät der
Rheinischen Friedrich-Wilhelms-Universität Bonn genehmigt.
Teile dieser Arbeit sind bereits veröffentlicht:
1. “A Novel Pyridine-Bridged Bis-benzimidazolylidene Pincer Palladium Complex:
Synthesis and Catalytic Properties”. Tu Tao, Jagadeesh Malineni, Karl Heinz Dötz, Adv. Synth.
Catal, 2008, 350, 1791-1795.
2. “A Lutidine-Bridged Bis-Perimidinium Salt: Synthesis and Application as a Precursor in
Palladium-Catalyzed Cross-Coupling Reactions”. Tao Tu, Jagadeesh Malineni, Xiaoling Bao
and Karl Heinz Dötz, Adv. Synth. Catal, 2009, 351, 1029-1034.
Members of the examination committee:
1. Prof. Dr. K. H. Dötz
2. Prof. Dr. A. Lützen
3. Prof. Dr. W. Mader
4. Prof. Dr. K. Maier
Tag der Promotion: 20.10.2011
Erscheinungsjahr: 2011
iii
It would not have been possible to write this doctoral thesis without the help and support of the
kind people around me, to only some of whom it is possible to give particular mention here.
My heart full thanks to my advisor Prof. Dr. Karl Heinz Dötz for giving me the wonderful
opportunity to work with him. It has been an honor to be his Ph.D student. I appreciate all his
precious and inspiring suggestions for my research. He has been invaluable on both an academic
and personal level, for which I am extremely grateful.
I am especially grateful to Prof. Dr. Arne Lützen for his acceptance as a co-referee for my
Ph.D viva. In addition I would like to acknowledge Prof. Dr. Werner Mader and Prof. Dr. Karl
Maier for their willingness to participate in the examination committee.
I am very much thankful to Dr. Tao Tu for giving his valuable suggestions during my
doctoral studies. My special thanks to Prof. Dr. Herwig Peterlik and Dr. Wilfried Assenmacher
for their great efforts to measure SAXS and TEM images of my samples.
I appreciate the kindness of Prof. Dr. Sigurd Höger for giving access to use the micro wave, DSC
and UV visible spectrophotometer. Especially I am thankful to Joscha Vollmeyer for both his
help and advice with the measurements.
I would like to acknowledge the Konrad Adenauer Stiftung for the financial support for my Ph.D
program and for giving me the opportunity to join the group meetings and seminar programs. I
am thankful to Dr. H.C. Berthold Gees and Prof. Dr. Heinrich Wamhoff for their valuable
suggestions and support.
My sincere thanks also goes to the NMR and mass spectrometry employees for their efforts with
measuring my samples. For the X-ray structure analysis I would like to thank Dr. Gregor
Schnakenburg for his help.
In addition, I would like to thank all my current and former colleagues of the working group for
their support and friendship. My special thanks goes to Dr. Jochen Möllmann for his kindness.
iv
And last, but definitely not least, I am forever indebted to my family and friends for their endless
patience, encouragement and support throughout my studies.
v
Contents
I. Introduction ................................................................................................................................. 1
II. Background 2
II.1 Types of Carbenes ............................................................................................................... 2
II.1.1 Fischer type carbene complexes ...................................................................3
II.1.2 Schrock type carbene complexes ..................................4
II.1.3 N-Heterocyclic carbenes ................................................................................................................5
II.1.3.1 Structure ................................................................................................................................. 5
II.1.3.2. Electronic effects ................................................................................................................... 6
II.1.3.2.1 Inductive effects .................. 6
II.1.3.2.2 Mesomeric effects ............................................................................................................... 6
II.1.3.2.3 Steric effects ........................ 7
II.1.3.2.4 Reactivity ............................................................................................................................. 8
II.1.4. Other metal complexes ................9
II.2 Gels ...................................................................................................................................... 10
II.2.1 Introduction ................................ 10
II.2.1.1 Classification of gels ............................................................................................................. 11
II.2.1.2 Primary structure.................. 11
II.2.1.3 Secondary structure ............................................................................................................. 12
II.2.1.4 Tertiary structure ................. 12
II.2.2 Examples ..................................................................................................................................... 13
II.2.2.1 Hydrogelators ....................................................................................................................... 13
II.2.2.1.1 Amphiphiles 14
II.2.2.1.2 Bolaamphiphiles (two-headed amphiphiles) .................................................................... 14