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Catalytic CH Activation of Benzene by Plantinum(II)

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Catalytic CH Activation of Benzene by Plantinum(II) Research Collection Doctoral Thesis Catalytic C-H activation of benzene by plantinum(II) a mechanistic study Author(s): Gerdes, Gerd Publication Date: 2004 Permanent Link: https://doi.org/10.3929/ethz-a-004830916 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library DISS. ETH No. 15631 Catalytic C-H Activation of Benzene by Platinum(II): A Mechanistic Study A dissertation submitted to the SWISS FEDERAL INSTITUTE OF TECHNOLOGY ZÜRICH for the degree of Doctor of Natural Sciences presented by Gerd Gerdes Diplom - Chemiker, Universität Heidelberg born July 3, 1973 citizen of Germany accepted on the recommendation of Prof Dr Peter Chen, examiner Prof Dr Antonio Togni, co-examiner 2004 Für Anja Es gibt viel zu verlieren, Du kannst nur gewinnen Genug ist zuwenig - oder es wird so wie es war Stillstand ist der Tod, geh voran, bleibt alles anders Der 1. Stein fällt aus der Mauer Der Durchbruch ist nah Herbert Grönemeyer Danksagung Mein besonderer Dank gilt Professor Dr. Peter Chen für das Überlassen des überaus spannenden Projekts, zahlreiche, inspirierende Diskussionen und wertvolle Anregungen. Zudem gewährte er mir stets den notwendigen wissenschaftlichen Freiraum, den ich sehr schätzte. Des Weiteren danke ich Professor Dr. Dietmar A. Plattner sehr herzlich für gründliche Diskussionen, sorgfältige Durchsicht des Manuskripts und gute Freundschaft. Bei Professor Dr. Antonio Togni bedanke ich mich herzlich für die Übernahme des Korreferats. Diese Arbeit enthielte nur halb so viele Resultate, hätte ich nicht stets ein offenes Ohr bei meinem Laborkollegen Dr. Christian Adlhart gefunden. Seinen Anregungen folgten einige wichtige Experimente und Auswertungen. Herrn Dr. Erich Meister bin ich zu Dank für Hilfe bei der Durchführung der UV/VIS Experimente sowie Diskussionen über korrekte Kinetiken verpflichtet. Genauso half mir Guido Grassi, die GC- MS Experimente durch zu führen. Weitere eingehende Diskussionen über die Geheimnisse der physikalischen Chemie verdanke ich Achim Sieben. André Müller danke ich für einige zum Teil verzwickte Synthesen, praktische Anregungen im Labor und Gesellschaft in der Mensa. Die Arbeit wäre gänzlich unmöglich gewesen, wenn nicht Rolf Dietiker meinen und alle anderen Computer am Laufen gehalten hätte. Für weiteres Korrekturlesen des Manuskripts bedanke ich mich bei Dr. Andreas Bach. Die gesamte Chen group hat mich mit einer freundlichen Atmosphäre unterstützt. Dafür danke ich Dr. Harold Baumann, Dr. Ruedi Hartmann, Dr. Daniel Lührs, Dr. Chrisian Hinderling, Dr. Derek Feichtinger, Dr. Thomas Gilbert, Prof. Dr. Ingo Fischer, Dr. Joëlle Vialon, Dr. Changkun Liu sowie den aktuellen Mitgliedern der Gruppe Eva Schön, Sanja Narancic, Dr. Loubna Hammad, Martin Jufer, Marc Bornand, Peter Zimmermann, Xueyi Chen, Dr. Xiangyang Zhang, Luca Cereghetti, Luca Castiglioni, Fabio di Lena, Claudio Gandolfo, Jonas Hostettler und nicht zuletzt Annette Ryter. Den Kristallographen des Instituts, Dr. Bernd Schweizer und Paul Seiler, danke ich für das Messen und Lösen der Kristallstrukturen. Mit ideenreichen Ratschlägen standen mir stets Prof. Dr. Bernhard Jaun als Leiter der NMR Abteilung sowie Dr. Walter Amrein als Leiter des MS Service zur Seite. Einige MS und UV/VIS Experimente wären nicht möglich gewesen, hätte René Dreier mir nicht die entsprechende Geräte gefertigt. Alle meine Arbeit verlöre ihren Sinn, wenn ich abends nicht meine wunderbare Frau Anja sehen könnte. Dank ihrer tatkräftigen Unterstützung und des ehrlichen Rückhalts konnte ich mich eingehend der Chemie widmen. Dem Fonds der Chemischen Industrie danke ich für die zwei Jahre währende Finanzierung. Parts of this work were published: Gerd Gerdes and Peter Chen, "Cationic Pt(II) Carboxlyato Complexes are Competent in Catalytic C-H Activation under Mild Conditions" Organometallics 2004, 23, 3031-3036. Gerd Gerdes and Peter Chen, "Comparative Gas-Phase and Solution-Phase Investigations of the Mechanism of C-H Activation by [(N-N)Pt(CH3)(L)]+" Organometallics 2003, 22, 2217-2225. Oral Presentations and Poster Presentations: 2003 XIV. Massenspektrometrische Diskussionsveranstaltung, Vienna, A (OP). Heidelberg Forum of Molecular Catalysis, University of Heidelberg, D (PP). XVth FECHEM Conference on Organometallic Chemistry, Zürich, CH (PP). 4th International School of Organometallic Chemistry, Camerino, I (OP). 2002 International Conference on Reactive Intermediates and Reaction Mechanism, Ascona, CH (PP). SFC Eurochem, Toulouse, F (OP). Gordon Conference on Organometallic Chemistry, Newport, USA (PP). 16th IUPAC Conference on Physical Organic Chemistry, UC San Diego, USA (OP). 2001 Meeting of scholarship holders of the FCI, University of Tübingen, Tübingen, D (OP). Fall Meeting of the New Swiss Chemical Society, University of Zürich, Zürich, CH (PP). Heidelberg Forum of Molecular Catalysis, University of Heidelberg, Heidelberg, D (PP). Contents Contents Abbreviations and Conventions IV Summary V Zusammenfassung VII 1 Introduction 1 1.1 Motivation 1 1.2 Platinum-mediated C-H Activation 1 1.3 Transition Metal Acetates in Hydrocarbon C-H Activation 6 1.4 Functionalization of Benzene and Methane through Heterobimetallic Catalysis 7 1.5 Electrospray Ionization Mass Spectrometry in Organometallic Chemistry 8 1.6 Gas-Phase Investigation of Pt-mediated C-H Activations 13 1.7 Density Functional Theory as a Tool in Organometallic Chemistry 14 2 The Solvent in Pt-mediated C-H Activations 16 2.1 Introduction 16 2.1.1 Syntheses 17 2.1.2 X-ray Crystallography 20 2.1.3 Quantum Chemical Methods 22 2.2 Gas-Phase Experiments 23 2.2.1 Intramolecular C-H, and C-F Activation in Tilset-like Platinum Complexes 24 2.2.2 Collision-Induced Dissociation of Isolated Cationic PtII Solvento Complexes 25 2.2.3 Coordination of Benzene to a Cationic PtII Center 29 2.2.4 Reaction of a cationic PtII Complex with Benzene in the Gas-Phase 30 2.2.5 Collision-Induced Dissociation of Cationic PtII Benzene Adducts with Argon, 2,2,2- Trifluoroethanol, and 1,1,1,2-Tetrafluoroethane 32 2.2.6 Scaling a Pirani Gauge for Diverse Collision Gases 33 2.2.7 Quantitative Comparison of PtII-mediated C-H Activation Reactions in the Gas Phase 34 2.2.8 Discussion 35 2.3 Solution-Phase Experiments 38 II 2.3.1 Benzene C-H Activation by Pt complexes in the Presence of 2,2,2-Trifluoroethanol 39 II 2.3.2 Benzene C-H Activation by Pt complexes in the Absence of 2,2,2-Trifluoroethanol 43 II 2.3.3 Activation Parameters for the C-H Activation of Benzene by a Pt complex 45 I Contents 2.3.4 Discussion 46 2.4 Conclusions 47 3 Scrambling in a Cationic PtII Complex in the Gas Phase 48 3.1 Deuterium Isotopic Scrambling in PtII Benzene Adducts in the Gas Phase 49 3.2 Installation of a Collision Cell in an Ion Trap 51 3.3 Theoretical Study of the Deuterium Isotopic Scrambling 52 3.4 Discussion 55 3.5 Conclusion 56 4 PtII-Acetato Complexes in Catalytic C-H Activation 57 4.1 Syntheses and Materials 57 II 4.2 Observation of Catalytic C-H Activation of Benzene by Pt 58 4.3 Acetic Acid-d4 as Deuterium Source 59 4.4 Kinetics of the Catalytic C-H Activation of Benzene by a PtII Complex 60 4.5 Gas-Phase Investigations of the Deuteration of Benzene catalyzed by PtII 62 4.6 Theoretical Study of the Intermediates of the Catalytic Deuteration 65 4.7 Discussion 66 4.8 Conclusion 70 5 Pt/Cu-catalyzed Functionalization of Benzene 71 5.1 Syntheses and X-Ray Crystallography 72 5.2 Variations on the Ullmann Reaction 75 5.3 Attempts to Fuse Catalytic Cycles 76 5.4 Gas-Phase Experiments with PtII/CuII Heterobimetallic Clusters 78 5.5 Discussion 82 5.6 Conclusion 83 6 Experimental Section 84 6.1 Instruments 84 6.2 Chemicals and Experimental Procedures 85 6.3 Ligand Syntheses. 86 6.4 Complex Syntheses. 87 6.5 Deuterated compounds and HBArF 91 6.6 Copper compounds 92 6.7 Crystallographic Data 93 II Contents 7 Appendix 95 7.1 Derivation of eq. 2.2 and Lambert-Beer's law 95 7.2 Principle of Linear Initial Rate 96 8 References 97 III Abbreviations and Conventions Abbreviations and Conventions API atmospheric pressure ionization (first region of all ESI instruments) CID collision-induced dissociation Da Dalton, equals unified atomic mass unit dau daughter scan mode DFT density functional theory ESI-MS electrospray ionization mass spectrometry eV electron Volt FT ICR-MS Fourier-transform ion cyclotron resonance mass spectrometry FWHM full width – half maximum GC-MS gas chromatography - mass spectrometry HiRes high resolution m/z mass-to-charge ratio NMR nuclear magnetic resonance r.t. room temperature rfd radio frequency voltage only daughter mode solv unspecified solvent molecule TFA trifluoroacetic acid TFE 2,2,2-trifluoroethanol THF tetrahydrofuran UV/Vis ultraviolet-visible spectroscopy VE valence electron Arabic numerals denote compounds that were synthesized by the author or used in syntheses. Lower case letters denote compounds that were computed by DFT methods. Capital letters denote chemical compounds that are quoted from literature. Roman numerals denote proposed or identified intermediates in reactions and catalytic cycles. For all compounds synthesized in the present work the lab journal page where the synthesis of the compound is described is given in the experimental section (GG n or André n). IV Summary Summary Hydrocarbons from oil and natural gas are the main feedstocks in the chemical industry. Thus, a direct, catalytic transformation of alkanes and arenes to functionalized compounds via C-H activation is of considerable interest and remains a challenge to chemists. A seminal achievement in this area was the homogeneous PtII-catalyzed C-H activation of benzene developed by Garnett and Hodges in the late 1960s. This reaction holds some mechanistic questions that have been addressed in the present work. The work is related to the better-known Shilov chemistry, the C-H activation of saturated hydrocarbons with concomitant formation of aliphatic alcohols, in that comparable intermediates and transition states are involved.
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