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Metalla affinity labels - a new route to organometallic enzyme hybrids [Elektronische Ressource] / Thomas Reiner

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TECHNISCHE UNIVERSITÄT MÜNCHEN Anorganisch-Chemisches Institut Metalla Affinity Labels – a New Route to Organometallic Enzyme Hybrids Thomas Reiner 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. Dr. h.c. mult. W. A. Herrmann 2. Univ.-Prof. Dr. M. Groll 3. Univ.-Prof. Dr. J. Buchner Die Dissertation wurde am 02.04.2009 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 11.05.2009 angenommen. Formyparents.Theyhavetaughtmethatknowledgeisnotaduty,butagift. ThisthesisoriginatedinthetimebetweenMay2006andApril2009attheAnorganischChemischesInstitutofTechnischeUniversitätMünchen.MyspecialthanksgotoDr.JörgEppingerMyspiritusrector,thanksforthisbothchallengingaswellasfascinatingtopic,yourabsolutetrustinmyskills,thankyoufortheinterestwhichyouhadinmyworkandforalltheseinvaluablescientificdiscussions,whichwerecrucialforthesuccessofthisthesis.SpecialthanksalsogotoProfessorDr.Dr.h.c.mult.

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Published 01 January 2009
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TECHNISCHE UNIVERSITÄT MÜNCHEN
Anorganisch-Chemisches Institut


Metalla Affinity Labels – a New Route to
Organometallic Enzyme Hybrids

Thomas Reiner


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. Dr. h.c. mult. W. A. Herrmann
2. Univ.-Prof. Dr. M. Groll
3. Univ.-Prof. Dr. J. Buchner





Die Dissertation wurde am 02.04.2009 bei der Technischen Universität
München eingereicht und durch die Fakultät für Chemie am 11.05.2009
angenommen.























For my parents.
They have taught me that knowledge is not a duty, but a gift.


This thesis originated in the time between May 2006 and April 2009 at the
Anorganisch-Chemisches Institut of Technische Universität München.









My special thanks go to

Dr. Jörg Eppinger

My spiritus rector, thanks for this both challenging as well as fascinating
topic, your absolute trust in my skills, thank you for the interest which you had in
my work and for all these invaluable scientific discussions, which were
crucial for the success of this thesis.


Special thanks also go to

Professor Dr. Dr. h. c. mult. Wolfgang A. Herrmann

Thank you very much for the possibility to work in your chair and for the
excellent infrastructure which I was allowed to use. Thank you also so much
for the interest in my research and for all the support which I was granted.




This thesis was supported by a scholarship of the Bayerische Eliteförderung. My very special thanks also go to:
Prof. Michael Groll for all the support, which I was granted from him and his chair.
Thank you for always giving me the feeling that I was one of your own PhD students.
Alexander Marziale and Anja Friedrich, what would I have done without you? Life in
the department of chemistry without you? Unimaginable!
Florian Kiefer, thank you so much for having been here all the time. Remember all
these nights working in the labs during our undergraduate studies? I am pretty sure they
wouldn’t have been half as much fun without you.
My colleagues Alice and Stefan Faul-Schlichtiger, who have made this PhD thesis a
happy and wonderful experience.
Ingrid Span and Björn Askevold, thanks for having become friends during the last
year. I am really proud of this next generation of PhD students in our labs.
Of course I will not forget my Bachelor Thesis students Dominik Jantke, Andreas
Raba and Markus Waibel. Without your passion and dedication to science and your
true interest in my topic, my thesis would not have become what it is like now.
Many thanks also to Ramona Lex. You have been such an enormous help during the
year you have spent in our labs. Furthermore, I probably would never have found the
epoxide crystals in that flask.
Andreas Frank, thank you for helping me recording and analyzing all these two-
dimensional NMR spectra.
Dr. Sven Schneider thanks for all the support, which I was granted from you and all
these scientific discussions which we have had during the last years.
Mr. Burghard Cordes and Mr. Helmut Krause for doing all the ESI MS and MALDI
TOF spectra. It has been a challenge first to analyze all these transition metal
complexes and enzyme hybrids. But you did a wonderful and remarkable job.
Dr. Eberhardt Herdtweck and Dr. Florian Kraus for doing all these crystal structural
analyses. None of my crystals has been textbook-perfect, I admit, but you have been
able to worm the structures out of these things.
Mrs. Ulrike Ammari and Mr. Thomas Tafelmaier for doing this plethora of elemental
analyses. I am still feeling a little bit sorry for keeping you busy so much during the last
2 ½ years. Mrs. Geta Krutsch for doing all these NMR spectra and being one of the nicest and
most positive-thinking person I have ever met.
Mrs. Irmgard Grötsch and Dr. Dimitrios Mihalios and all the staff in our chair. Without
your work, research would not be possible the way it is now.
I would also like to thank the many other researchers from the Department Chemie.
Most of you have become friends over the years. I can hardly imagine a nicer institute to
have conducted my PhD thesis in.















This thesis would definitely not have been possible without:

I cannot imagine, what my life would be like without Andreas Binder, Michael Blümel,
Dominik Kreuzer and Martin Seitz. I now know you guys for more than 20 years. You
are not only friends any more, you are family.
Virginia Roberts how can I ever thank you? Thanks for making me part of your life.
I truly love you!
Dominik and Maximilian Reiner, my brothers. Without you, I wouldn’t have become
the person which I am now. You have made my whole life a positive experience.
Mom and Dad. There are no words for all the gratefulness which I am feeling towards
my loving parents.
Abbreviations

abs. absolute
Ac acetyl
ACN acetonitrile
AcOH acetic acid
AcOEt acetic acid ethyl ester
Ar aryl
BAPNA α-N-Benzoyl-DL-arginine p-nitroanilide
BuLi butyl lithium
Boc di-tert-butyl dicarbonate
Bzl benzyl
Cp cyclopentadienyl
Cp* pentamethyl cyclopentadienyl
CV cyclic voltametry
δ chemical shift (ppm)
DAST (diethylamino)sulfur trifluoride
DCM dichloromethane
DMF dimethylformamide
DMSO dimethylsulfoxide
eq. equivalent
EDCI 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride
Et N triethylamine 3
EtOH ethanol
Et O diethyl ether 2
ESI electron spray ionization
GC gas chromatography
h hour(s)
HOPfp 2,3,4,5,6-pentafluorophenole
HSQC heteronuclear spin quantum correlation
i
Pr Isopropyl
M molar
m-Al metalla affinity label
Me methyl
MeOH methanol
MHz megahertz
min minute(s)
mL milliliter(s)
MS mass spectrometry
NHS N-hydroxy succinimide
NMR nuclear magnetic resonance
o ortho
OAc acetate
tO Bu tert.-butanolate
OMEH organometallic enzyme hybrid
TsOH toluene sulfonyl
p para
Ph phenyl
ppm parts per million
PS polystyrene
py pyridine
RT room temperature
s second(s)
SS-DCC N-Cyclohexylcarbodiimide, N'-methyl polystyrene
Suc succinimide
TFA trifluoro acetic acid
THF tetrahydrofurane
TOF turn over frequency