Application of rhenium and ruthenium organometallic complexes in carbonyl olefination [Elektronische Ressource] / Filipe Miguel Esteves Pedro

Filipe Pedro

Informations

• Publié par: technische_universitat_munchen
• Publié le: 01 janvier 2007
• Nombre de lectures: 24
• Langue: English
• Poids de l'ouvrage: 3 Mo

Extrait

Lehrstuhl für Anorganische Chemie
Technische Universität München


Application of Rhenium and Ruthenium Organometallic
Complexes in Carbonyl Olefination



Filipe Miguel Esteves Pedro


Vollständiger Abdruck der von der Fakultät für Chemie der Technischen
Universität München zur Erlangung des akademischen Grades eines

Doktors der Naturwissenschaften

genehmigten Dissertation



Vorsitzender: Univ. -Prof. Dr. K. Köhler
Prüfer der Dissertation: 1. Univ. -Prof. Dr. F. E. Kühn
2. Univ. -Prof. Dr. O. Nuyken, i. R.














Die Dissertation wurde am 28.02.2007 bei der Technischen Universität München
eingereicht und durch die Fakultät für Chemie am 26.03.2007 angenommen. Die vorliegende Arbeit entstand in der Zeit von April 2003 bis Februar 2007 am
Anorganisch-chemischen Institute der Technischen Universität München





I would like to express my deep gratitude to my academic supervisor

Univ.-Prof. Dr. Fritz E. Kühn

For giving me the opportunity to work in his group, his continuous supervision,
encouragement and confidence in me and my work






























Diese Arbeit wurde durch die Fundação Gulbenkian and the Fundação para a Ciência e
a Tecnologia (FCT) gefördet.
Gedruck mit Unterstützung des Fundação para a Ciência e a Tecnologia (FCT).
Acknowledgements
Acknowledgements

I would like to express my deep gratitude to my supervisor, Prof. Fritz E. Kühn for the
continuous support, trust and his tireless efforts to help me improve my work with
insightful ideas and suggestions that were decisive to the success of my Ph.D. I also
acknowledge his help in my everyday life especially the support to adapt to life in
Munich.

I thank Prof. Walter Baratta for giving me the opportunity to work in his group in
Università di Udine and the fruitful cooperation we developed. I also thank the warmth
of himself and his group during my stays in Udine.
I thank Prof. János Mink and his group for the interesting work developed during my
stay in Budapest and Vezprém and the help provided in the DRIFT mesurements.

I had the luck of working with an excellent team at both scientific and human level. I
want to thank Dr. Ana Santos Kühn for introducing me to the catalytic aldehyde
olefination field, for sharing with me her scientific excellence through our many
collaborations. I also thank her friendship and for always being helpful in solving
everyday problems, which made my life much easier.
Dr. Klaus Ruhland is acknowledged for his help with the NMR experiments, with
helpful discussions and excellent suggestions to my work. His passion to chemistry was
a real lesson that I take with me for my future projects.
Dr. Yanmei Zhang is acknowledged for introducing me to the rest of Prof. Kühn’s
group, for making me feel “at home” and for starting with me the “Mensa group” that
helped built a true team spirit. I thank Dr. Jin Zhao for the good friendship both in lab
and outside in the real life. Her teachings and dedication to work were great examples
for me that I won’t forget. I thank Dr. Ayyamperumal Sakthivel for the good teamwork,
friendship and useful discussions to improve our cooperation. I thank Dr. Wei Sun for
the helpful discussions about the aldehyde olefination topic and his useful suggestions
to my work. To all my colleagues, Dr. Jörg Fridgen, Dr. Ahmed Hijazi, Dr. Marta
Abrantes, Syukri, Akef Al-Hmaideen, Dr. Christelle Freund, Dr. Xiangge Zhou, Dr. Chi
Zhang, Tommy Reiner, Khatarina Nikolaides, Alice Schlichtiger, Katja Siega (Udine),
Acknowledgements
Micaela Toniutti (Udine), Lázló Hajba (Veszprém) and all my students a huge thank
you for your help in the lab, good disposition and interesting discussions we had.
I thank Frau Georgeta Krutsch, “Geta”, for the support in the TG-MS and NMR
experiments and for always being so nice. I appreciate the help of Frau Sabina Mühl
with the GC and GC-MS measurements. I also thank Hern Barth and Frau Ammari for
the Elemental Analysis of my compounds.

I thank the whole football team for all the great games and the funny discussions about
football, the never-ending subject, especially my good friends Jörg Fridgen, Ahmed,
Syukri and Akef and the great captain Klaus Ruhland.

To the “other” friends I found in Munich: Pedro, Gonçalo, Catarina, Angela Tan, Maria
Sudupe, Christelle Freund, Arnaud Dupays, I will not forget the good times we spent
together and I will treasure our friendship even if life takes us to different places.

I thank the Fundação Gulbenkian and the Fundação para a Ciência e a Tecnologia
(FCT) for the research grants that supported my PhD.

I thank Marta for always being there for me and all the love and great moments we
shared in the last two years.
Finally I thank a wonderful family: my mother, my father, my brother, all my
grandparents, and my cousins, for always supporting me and giving me strength to carry
on.



Abbreviations
Abbreviations

4-nba 4-nitrobenzaldehyde
AO aldehyde olefination
Brij-30 1,3-diacetoxy-1,1,3,3-tetrabutyltin oxide polyethylene glycol dodecyl ether
Cp cyclopentadienyl
Cp* pentamethylcyclopentadienyl
CTABr hexadecyl-trimethyl ammonium bromide
Cy cyclohexyl
chemical shift (ppm) δ
doublet d
ethyldiazoacetate EDA
elemental analysis EA
gas chromatography coupled with mass spectroscopy GC-MS
figure Fig.
multiplet m
methyl Me
methyltrioxorhenium MTO
nuclear magnetic resonance NMR
room temperature RT
room temperature ionic liquid RTIL
singlet s
triplet t
transmission electron microscopy TEM
tetraethyl orthosilicate TEOS
thermogravimetric analysis TGA
thermogavimetry coupled with mass spectroscopy TG-MS
tetrahydrofuran THF
tetramethyl ammonium hydroxide TMAOH
turn over frequency TOF
turn over number TON
X-ray diffraction XRD

Index
Index

1. Introduction 1
1.1 Wittig reaction: Overview 1
1.2 Variations to the Wittig reaction 2
1.3 Scope and limitations of the Wittig reaction and its variants 3
1.4 Organometallic alternatives to the Wittig reaction 3
1.5 Catalytic aldehyde olefination 4
1.5.1 Rhenium based catalytic aldehyde olefination 6
1.5.2 Catalytic generation of stabilized ylides 10
1 21.5.3 Carbon-carbon bond formation catalysed by Cp’RuXL L
complexes 14
1.5.4 Immobilization of Re and Ru catalysts 16
1.5.5 Methylenation of carbonyl compounds 18
1.6 Objectives 20
2. Oxorhenium Complexes as Aldehyde Olefination Catalysts 22
2.1 Background 22
2.2 Results and discussion 23
2.2.1 Survey of Re-oxo complexes for aldehyde olefination catalysis 23
2.2.2 The influence of the substrates on the catalytic performance of
2 26 ReMeO ( η -alkyne) complexes 2
35 2.3 Conclusions
37 3. Catalytic Ketone Olefination with Methyltrioxorhenium
37 3.1 Background
37 3.2 Results and discussion
4. Organometallic Ruthenium Complexes: Application in the
41 Olefination of Carbonyl Compounds
41 4.1 Background
42 4.2 Results and discussion
42 4.2.1 Catalyst optimization
46 4.2.2 Aldehyde and ketone olefination with compound 7
50 4.3 Conclusions

Index
5. Investigations on the reaction mechanism of catalytic carbonyl
olefination with Cp*RuCl(PPh ) 51 3 2
5.1 Background 51
5.2 Results and discussion 51
5.3 Conclusion 59
5 6. Heterogenization of ( η -C Me )Ru(PPh )Cl and its catalytic 5 5 3 2
60 application for cyclopropanation of styrene using ethyl diazoacetate
60 6.1 Background
62 6.2 Results and Discussion
69 6.3 Conclusions
7. Grafting of Cyclopentadienyl Ruthenium Complexes on aminosilane
70 linker modified mesoporous SBA-15 silicates
70 7.1 Background
72 7.2 Results and Discussion
80 7.3 Conclusions
81 8. Experimental section
81 8.1 General procedure
81 8.1.1 Inert gas atmosphere
81 8.1.2 Solvents
81 8.2 Characterization methods
82 8.3 Synthesis and characterization of the compounds described in this work
82 8.3.1 Chapter 2
83 8.3.2 Chapter 3
83 8.3.3 Chapter 4
84 8.3.4 Chapter 5
85 8.3.5 Chapter 6
87 8.3.6 Chapter 7
88 8.4 Catalytic reactions
88 8.4.1 General procedure for aldehyde olefination
88 8.4.2 General procedure for ketone olefination
89 8.4.3 General procedure for styrene cyclopropanation
89 8.4.4 Mechanistic studies
90 9. Summary
96 References
Chapter 1