Pyrimidine Functionalized Phosphine Ligands and Their homogeneous catalysts. 1.2. Ligands in Transition

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  • Pyrimidine Functionalized Phosphine Ligands and

    Their Application in Catalysis

    Dissertation zur Erlangung

    des Doktorgrades der Naturwissenschaften (Dr. rer. nat.)

    genehmigt vom Fachbereich Chemie

    der Technischen Universität Kaiserslautern

    (D 386)

    Vorgelegt von

    MSc Saeid Farsadpour

    Betreuer der Arbeit: Prof. Dr. W. R. Thiel

    Tag der wissenschaftlichen Aussprache: 10.09.2012

  • Vom Fachbereich Chemie der Technischen Universität Kaiserslautern am 10.09.2012 als

    Dissertation angenommen.

    Dekan: Prof. Dr.-Ing. Jens Hartung

    Vorsitzender der Prüfungskommission: Prof. Dr. H. Sitzmann

    1. Berichterstatter: Prof. Dr. W. R. Thiel

    2. Berichterstatter: Prof. Dr. S. Ernst

  • Die vorligende Arbeit wurde im Fachbereich Chemie der Technischen Universität

    Kaiserslautern im Arbeitskreis von Prof. Dr. W. R. Thiel in der Zeit von August 2008 bis

    August 2012 angefertigt.

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  • Abbreviations

    AAS atomic absorption spectrometry

    Å angstrom

    Anal. analytical

    a.u Arbitrary Unis

    BET Brunauer-Emmet-Teller

    BJH Barrett-Joyner-Halenda

    br. broad

    °C degrees centigrade

    calc. calculated

    CID collision-induced dissociation

    CP MAS Cross Polarization Magic Angle Spinning

    d doublet

    DFT density functional theory

    DMF N,N-dimethylformamide

    DMF-DMA N,N-dimethylformamide dimethyl acetal

    DMSO dimethyl sulfoxide

    eq equivalent

    eq. equation

    ESI-MS electrospray mass spectrometry

    Et ethyl

    Et2O diethyl ether

    EtOH ethanol

    FT-IR fourier transform infrared spectroscopy

    g gram

    GC gas chromatography

    h hour

    Hz hertz

    iPr isopropanol

    IR infrared

    J coupling constant

    kcal kilocalorie

    M molar

  • m multiplet

    MCM Mobil Crystalline Material

    Me Methyl

    ml millilitre

    NMR nuclear magnetic resonance

    Ph Phenyl

    ppm parts per million

    ref. reference

    refl. Reflux

    RT room temperatur

    s Singlet

    SEM Scanning Electron Microscopy

    T temperature in Kelvin

    TEM Transmission Electron Microscopy

    T Triplet

    tBu tert-Butyl

    temp. temperature in °C

    TG-DTG Thermogravimetric and Differential Thermogravimetric analysis

    THF tetrahydrofuran

    TOF turn over frequency

    TON turn over number

    TPP triphenylphosphine

    XRD X-ray diffraction

    ʋ͂ wave number in cm-1

    δ chemical shift in ppm

  • Contents

    Abbreviations...............................................................................................................................................................

    1. Introduction ....................................................................................................................................................... 1

    1.1. Catalysis ................................................................................................................................................... 1

    1.1.1. Types of Catalysts ........................................................................................................................... 2

    1.1.2. Heterogenization of Homogeneous Catalysts .................................................................................. 2

    1.2. Ligands in Transition Metal Catalysis ...................................................................................................... 3

    1.2.1. Phosphorus-containing Ligands ...................................................................................................... 4

    1.3. Palladium-Catalyzed Reactions in Presence of Phosphine Ligands. ...................................................... 10

    2. Motivation ....................................................................................................................................................... 13

    3. Results and Discussion .................................................................................................................................... 17

    3.1. Ligand Synthesis .................................................................................................................................... 17

    3.1.1. Synthesis of the Pyrimidinyl Functionalized Phosphine Ligands .................................................. 17

    3.1.2. Synthesis of Multidentate Ligands ................................................................................................ 35

    3.2. Complex Synthesis ................................................................................................................................. 46

    3.2.1. Palladium Complexes with Pyrimidinylphosphine Ligands Containing Primary and Secondary

    Amino Groups ................................................................................................................................................. 48

    3.2.2. Palladium Complexes of Pyrimidinylphosphine Ligands with a Tertiary Amino Group .............. 51

    3.2.3. DFT Calculations .......................................................................................................................... 59

    3.2.4. Synthesis of a Palladium Complex with a Para Substituted Pyrimidinylphosophine Ligand. ...... 60

    3.2.5. Palladium Complexes with Pincer-Type PNN and PN Ligands Based on 3-Amino-

    pyrimidyl pyridine ........................................................................................................................................... 64

    3.3. Homogeneous Catalytic Experiments .................................................................................................... 80

    3.3.1. Catalytic Activities ........................................................................................................................ 83

    3.4. Covalently Supported Pyrimidinylphosphine Palladacycles as a Heterogenized Catalysts for the

    Suzuki–Miyaura Cross Coupling. ........................................................................................................................ 88

    3.4.1. Introduction ................................................................................................................................... 88

    3.4.2. Preparation of the Heterogeneous Catalysts 26@MCM-41 and 26@SiO2 .................................... 97

    3.4.3. Characterization of the Heterogeneous Catalysts 26@MCM-41 and 26@SiO2 ............................ 98

    3.4.4. Catalysis ...................................................................................................................................... 108

    3.4.5. Reusability of the Catalysts 26@MCM-41 and 26@SiO2 ........................................................... 111

  • 3.5. A Covalently Supported Palladium Complex Bearing a 4-(2-Amino)pyrimidinyl Functionalized

    Triphenylphosphine Ligand. .............................................................................................................................. 114

    3.5.1. Introduction ................................................................................................................................. 114

    3.5.2. Preparation of the Heterogeneous Catalysts 28@MCM-41 and 28@SiO2 .................................. 123

    3.5.3. Catalysis ...................................................................................................................................... 134

    3.5.4. Reusability of the Catalysts 28@MCM-41 and 28@SiO2 ........................................................... 136

    4. Conclusion and Outlook ................................................................................................................................ 139

    5. Experimental .................................................................................................................................................. 143

    5.1. Materials ............................................................................................................................................... 143

    5.2. Characterization of Precursors, Ligands and Complexes ..................................................................... 143

    5.3. Characterization of Hybrid Materials ................................................................................................... 144

    5.4. Ligand Synthesis .................................................................................................................................. 145

    5.5. Complex Synthesis ............................................................................................................................... 171

    5.6. Synthesis of Hybrid Materials .............................................................................................................. 178

    6. References ....................