La lecture à portée de main
Découvre YouScribe en t'inscrivant gratuitement
Je m'inscrisDécouvre YouScribe en t'inscrivant gratuitement
Je m'inscrisDescription
Informations
Publié par | technische_universitat_munchen |
Publié le | 01 janvier 2009 |
Nombre de lectures | 23 |
Langue | English |
Poids de l'ouvrage | 3 Mo |
Extrait
Technische Universit¨at Mu¨nchen
Lehrstuhl fu¨r Anorganische Chemie
Synthesis and characterization of
heterogeneous rhenium and
molybdenum catalysts. Applications in
olefin metathesis and olefin epoxidation
Draganco Veljanovski
Vollst¨andiger Abdruck der von der Fakult¨at fu¨r Chemie der Technischen Universit¨at Mu¨nchen
zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften
genehmigten Dissertation.
Vorsitzender: Univ.-Prof. Dr. Fritz E. Ku¨hn
Pru¨fer der Dissertation:
1. Univ.-Prof. Dr. Dr. h. c. mult. Wolfgang A. Herrmann
2. Prof. Dr. Jean-Marie Basset (em.),
Universit´e Claude Bernard Lyon / Frankreich
Die Dissertation wurde am 14.01.2009 bei der Technischen Universit¨at Mu¨nchen eingereicht
und durch die Fakult¨at fu¨r Chemie am 10.03.2009 angenommen.To My FamilyIf A is success in life, then A equals X plus Y plus Z. Work is X; Y is play; and Z is keeping
your mouth shut.
Albert Einstein (1879 - 1955)Die vorliegende Arbeit entstand in der Zeit vom April 2005 bis January 2009 am
Anorganisch-chemischen Institut der Technischen Universit¨at Mu¨nchen
I would like to express my deep gratitude to my academic supervisor
Prof. Dr. Dr. h. c. mult. Wolfgang A. Herrmann
for his trust, advice, interesting discussions and
the continuous support of my work.V
Acknowledgment
I am very grateful to Prof. Fritz E. Ku¨hn for his support during these years. His continu-
ous encouragement, constructive comments and trust in me and my projects made this work
possible.
The most intensive and rewarding cooperation during my Ph. D. has without doubt been
with Dr. Christophe Cop´eret. His enthusiasm, patients and working ethic were essential
for the success of our metathesis project. Despite the chalange posed by the distance between
Lyon and Munich, he was always only a phone call away when I was in a need of advice or a
trusted opinion.
I am deeply grateful to Dr. Klaus Ruhland who strongly influenced my work with many
helpful suggestions and fruitfull discussions. He didn’t only improved my scientific work but
also accompanied me as a friend as well.
I am also very grateful to Prof. Peter H¨arter who offered me the chance to pursue
the research in heterogeneous catalysis by arranging for me to go to Lyon in Laboratoire de
Chimie Organom´etallique de Surface for my metathesis project. All the thanks to Gabriele
Raudaschl-Sieber for her patience while recording my solid-state NMR spectra. Also many
thanks to Dr. Sven Schneider who helped me a lot with my deuterium spectra in solution
which are also part of this work. I am sending many thanks toDr. Ahmad Al-Ajlouni from
the Jordan University of Science and Technology for his constant support during our kinetic
studies of the oxidation of CpMo(CO) CH .3 3
All the thanks to Dr. Eberhardt Herdtweck for the X-ray structural determination
includedinthisthesis. IamalsothankfultotheelementalanalysislaboratoryoftheTechnische
Universit¨at Mu¨nchen for their contribution to this work. To Mrs. Georgeta Krutsch for
the NMR measurement and the TG-MS measurements, and Thomas Schr¨ofel for his kind
assistance in the GC laboratory.VI
ManythankstomylaboratorycolleagueDr. EckhartLouisforkeepingtheperfectworking
atmosphere in our laboratory. His various theoretical as well as practical suggestions revolu-
tionize my preparative work. I also thank to Alejandro Capape Miralles and Evangeline
Tosh for reading and correcting parts of this thesis, as well as for our creative discussions in
between the working hours.
Mrs. Gr¨otsch, Mrs. Kaufmann, and Mrs. Schuhbauer from the secretary’s office are
acknowledged for their help with the organizations of all kinds and various burocratic matters
during this period.
AndfinallyallthethankstoallmycolleaguesinProf. Herrmann’sandProf. Ku¨hn’sgroupfor
the nice working atmosphere in the university, their cooperation and help. Also many thanks
to my colleagues in Laboratoire de Chimie Organom´etallique de Surface in Lyon, especially
David Gajan, for helping me to adapt to the new laboratory environment. Also many thanks
to Raphael Wischert who continued with the practical work after I left.Contents VII
Contents
Abbreviations 1
1. Introduction 3
1.1. Industrial catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2. Heterogeneous and homogeneous catalyst . . . . . . . . . . . . . . . . . . . . . . 7
1.3. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
I. Epoxidation 11
2. Introduction 13
2.1. Rhenium catalysts in the epoxidation of olefins. . . . . . . . . . . . . . . . . . . 16
2.1.1. Dirhenium heptaoxide and derivatives. . . . . . . . . . . . . . . . . . . . 16
2.1.2. The carboxylato rhenium complexes . . . . . . . . . . . . . . . . . . . . 17
2.1.3. MTO synthesis and useage as epoxidation catalyst . . . . . . . . . . . . 20
2.1.4. MTO as a heterogeneous catalyst . . . . . . . . . . . . . . . . . . . . . . 23
2.2. Molybdenum catalysts in the epoxidation of olefins . . . . . . . . . . . . . . . . 26
2.2.1. Dioxomolybdenum(VI) complexes with Mo-C σ-bonds . . . . . . . . . . 26
2.2.2. Dioxomolybdenum(VI) complexes with cyclopentadienyl ligands . . . . . 27
2.2.3. Mechanistic insights into the epoxidation with molybdenum catalysts. . . 33
3. Synthesis of a novel heterogeneous rhenium catalyst for olefin epoxidation 39
3.1. Mobil crystalline of materials (MCM) . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2. The grafting of acylperrhenate on mesoporous sieves. . . . . . . . . . . . . . . . 40
3.2.1. A model of the grafting process . . . . . . . . . . . . . . . . . . . . . . . 43VIII Contents
3.2.2. Catalytic applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4. Kinetic studies on the oxidation of CpMo(CO) CH 493 3
4.1. Reaction of CpMo(O )OCH with TBHP . . . . . . . . . . . . . . . . . . . . . . 542 3
4.2. Catalytic epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2.1. Epoxidation catalyzed by CpMo(CO) CH . . . . . . . . . . . . . . . . . 573 3
4.2.2. Epoxidation catalyzed by CpMo(O )OCH . . . . . . . . . . . . . . . . . 592 3
4.2.3. Epoxidation catalyzed by CpMoO CH . . . . . . . . . . . . . . . . . . . 632 3
II. Olefin metathesis 65
5. Introduction 67
5.1. Mechanistic studies and the development of organometallic catalysts . . . . . . . 72
5.1.1. The elucidation of the olefin metathesis mechanism . . . . . . . . . . . . 72
5.1.2. The discovery and development of the Schrock catalyst . . . . . . . . . . 74
5.1.3. The discovery and development of the Grubbs catalyst . . . . . . . . . . 78
5.2. Heterogeneous catalysts in the olefin metathese . . . . . . . . . . . . . . . . . . 82
5.2.1. Olefin metathesis catalystst on silica surfaces . . . . . . . . . . . . . . . . 83
5.2.2. MTO on γ - Al O . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86-(500)2 3
5.2.3. The reaction mechanism and deactivation pathways . . . . . . . . . . . . 90
6. CpMo(CO) CH /γ-Al O , a heterogeneous catalyst for olefin metathesis 93-(500)3 3 2 3
6.1. An estimation of the pKa-Value of CpMo(CO) CH . . . . . . . . . . . . . . . . 933 3
6.2. Spectroscopic characterization of CpMo(CO) CH on γ-Al O . . . . . . . . 96-(500)3 3 2 3
6.2.1. IR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6.2.2. Mass balance analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6.2.3. Solid state NMR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 97
6.3. Propene metathesis with CpMo(CO) CH on γ-Al O . . . . . . . . . . . . 101-(500)3 3 2 3
136.3.1. Metathesis of C-di-labeled ethene with CpMo(CO) CH on γ-Al O 104-(500)3 3 2 3
7. (CH ) ReO on γ-Al O , a heterogeneous catalyst for olefin metathesis 107-(500)3 3 2 2 3
7.1. Spectroscopic characterization of (CH ) ReO on γ-Al O . . . . . . . . . . 108-(500)3 3 2 2 3Contents IX
7.1.1. IR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
7.1.2. Mass balance analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
7.1.3. NMR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
7.2. Propene metathesis with (CH ) ReO on γ-Al O . . . . . . . . . . . . . . . 109-(500)3 3 2 2 3
7.3. Propene metathesis with (CH ) ReO on γ-Al O in a flow reactor . . . . . 110-(500)3 3 2 2 3
III.Experimental procedures 117
8. General procedures 119
8.1. IR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
8.2. NMR spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
8.3. The power X-ray diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
8.4. The low temperature N adsorption/desorption isotherms . . . . . . . . . . . . . 1202
9. The synthesis of the catalyst precursors 123
9.1. Preparation of CpMo(O) OCH . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232 3
9.2. Single crystal determination of CpMo(O )OCH . . . . . . . . . . . . . . . . . . 1232 3
139.3. Preparation of CpMo( CO) CH . . . . . . . . . . . . . . . . . . . . . . . . . . 1243 3
139.4. Preparation of CpMo(CO) CH . . . . . . . . . . . . . . . . . . . . . . . . . . 1253 3
9.5. Preparation of trimethylsilyl perrhenate . . . . . .