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Raman Spectroscopic Studies of Group 8 Metallocenes and Halogen-Bonded Cocrystals

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Raman Spectroscopic Studies of Group 8 Metallocenes and Halogen-Bonded Cocrystals Raman Spectroscopic Studies of Group 8 Metallocenes and Halogen-Bonded Cocrystals Yann Desjardins-Langlais Department of Chemistry Faculty of Science McGill University, Montreal August 2014 A thesis submitted to McGill University in partial fulfillment of the requirements of the degree of Master of Science © Yann Desjardins-Langlais 2014 Table of Contents List of Tables ........................................................................................................ iv List of Figures .........................................................................................................v Abstract ................................................................................................................ vii Résumé ................................................................................................................ viii Acknowledgements .............................................................................................. ix Chapter 1: Introduction ........................................................................................1 Chapter 2: Methodology........................................................................................3 2.1 Raman Spectroscopy ......................................................................................3 2.2 Raman Instruments and Applications ............................................................6 2.3 Symmetry and Factor Group Analysis.........................................................10 2.4 Diamond-anvil Cells ....................................................................................12 2.5 Pressure Calibration Methods ......................................................................14 2.6 Raman Experimental Setup .........................................................................15 Chapter 3: Background Literature ....................................................................18 3.1 Group 8 Metallocenes ..................................................................................18 3.1.1 Ferrocene ...............................................................................................20 3.1.2 Ruthenocene ..........................................................................................24 3.1.3 Osmocene ..............................................................................................26 3.2 Halogen-bonding in Cocrystals ...................................................................27 3.2.1 Cocrystal Properties ..............................................................................27 3.2.2 Halogen Bonding ..................................................................................28 3.2.3 Halogen-Bonded Cocrystals .................................................................29 3.2.4 Raman Spectroscopy and Halogen Bonding .........................................30 Chapter 4: Raman Spectroscopic Studies of Group 8 Metallocenes ...............33 5 4.1 Ferrocene, (η -C5H5)2Fe ..............................................................................33 4.1.1 Raman Spectra Assignments .................................................................33 4.1.2 Variable-temperature Raman Spectra ...................................................35 4.1.3 Variable-pressure Raman Spectra .........................................................39 ii 5 4.2 Ruthenocene, (η -C5H5)2Ru .........................................................................44 4.2.1 Raman Spectra Assignments .................................................................44 4.2.2 Variable-temperature Raman Spectra ...................................................47 4.2.3 Variable-pressure Raman Spectra .........................................................50 5 4.3 Osmocene, (η -C5H5)2Os .............................................................................54 4.3.1 Raman Spectra Assignments .................................................................54 4.3.2 Variable-temperature Raman Spectra ...................................................56 4.3.3 Variable-pressure Raman Spectra .........................................................59 Chapter 5: Effect of Pressure on Halogen Bonding in Cocrystals ..................63 5.1 Cocrystal Components .................................................................................63 5.2 (MDPPO)2•TFBB ........................................................................................65 5.3 (MDPPO)2•TFIB ..........................................................................................71 Chapter 6: Conclusions .......................................................................................77 References .............................................................................................................81 Appendix A Point Group Tables ........................................................................86 Appendix B Curve Fitting Using Wire 3.4.........................................................90 iii List of Tables 4.1.1 Raman peak assignments of ferrocene .......................................................34 4.1.2 Pressure shifting rates of ferrocene Raman peaks .....................................43 4.2.1 Raman peak assignments of ruthenocene ..................................................46 4.2.2 Pressure shifting rates of ruthenocene Raman peaks .................................53 4.3.1 Raman peak assignments of osmocene ......................................................55 4.3.2 Pressure shifting rates of osmocene Raman peaks ....................................62 5.2.1 Raman peaks of MDPPO, TFBB and the 2:1 cocrystal .............................66 5.2.2 Raman peaks and pressure shifting rates of TFBB cocrystal ....................70 5.3.1 Raman peaks of MDPPO, TFIB and the 2:1 cocrystal ..............................71 5.3.2 Raman peaks and pressure shifting rates of TFIB cocrystal ......................75 iv List of Figures 2.1.1 Differences between Rayleigh and Raman scattering .................................4 2.1.2 Stokes and anti-Stokes intensities versus Rayleigh scattering .....................6 2.2 Schematic representation of a Raman microscope ......................................9 2.4 Representation of a diamond-anvil cell with gasket ..................................13 2.5 Ruby fluorescence spectrum upon 514.5 nm excitation ............................14 2.6.1 Raman spectrometer set-up ........................................................................16 2.6.2 Inside view of Raman spectrometer set-up ................................................17 3.2 Examples of bonding interactions between MDPPO and TFIB ................32 4.1.1 Ferrocene Raman spectra recorded with 514.5 and 785 nm lasers ............33 4.1.2 Ferrocene Raman spectra at various temperatures .....................................37 4.1.3 Ferrocene spectra of C-H stretching region at various temperatures .........37 4.1.4 Ferrocene Raman peak positions at different temperatures .......................38 4.1.5 Ferrocene spectra at various pressures in 100-1265 cm-1 region ...............39 4.1.6 Ferrocene spectra in the C-H stretching region at various pressures .........40 4.1.7 Ferrocene Raman peak positions at different pressures .............................42 4.2.1 Ruthenocene Raman spectra recorded with 514.5 and 785 nm lasers .......45 4.2.2 Ruthenocene Raman spectra at various temperatures ................................48 4.2.3 Ruthenocene C-H stretching region at various temperatures ....................48 4.2.4 Ruthenocene Raman peak positions at different temperatures ..................49 4.2.5 Ruthenocene spectra at various pressures in 100-1265 cm-1 region ..........50 4.2.6 Ruthenocene spectra at various pressures in C-H stretching region ..........51 4.2.7 Ruthenocene Raman peak positions at various pressures ..........................52 4.3.1 Osmocene Raman spectra recorded with 514.5 and 785 nm lasers ...........54 4.3.2 Osmocene Raman spectra at various temperatures ....................................57 4.3.3 Osmocene spectra at various temperatures in the C-H stretching region ..57 4.3.4 Osmocene peak positions at various temperatures ....................................58 4.3.5 Osmocene spectra at various pressures in 100-1265 cm-1 region ..............59 4.3.6 Osmocene spectra at various pressures in C-H stretching region ..............60 v 4.3.7 Osmocene peak positions at various pressures ..........................................61 5.1.1 Raman spectrum of MDPPO taken with 514.5 nm laser ...........................63 5.1.2 Raman spectrum of TFBB taken with 514.5 nm laser ...............................64 5.1.3 Raman spectrum of TFIB taken with 514.5 nm laser ................................64 5.2.1 Raman spectrum of (MDPPO)2•TFBB cocrystals ....................................65 5.2.2 Pressure spectra of TFBB cocrystal in 100-1265 cm-1 region ...................67 5.2.3 Pressure spectra of TFBB cocrystal in 1365-3500 cm-1 region .................68 5.2.4 Raman peak positions of TFBB cocrystal at various pressures .................69 5.3.1 Pressure spectra of TFIB cocrystal in 100-1265 cm-1 region ....................72 5.3.2 Pressure spectra of TFIB cocrystal in 1365-3500 cm-1 region ..................73 5.3.3 Raman peak positions of TFIB cocrystal at various pressures ..................74 vi Abstract Raman spectroscopy has been used on two different types of crystalline materials: group eight metallocenes and halogen-bonded cocrystals. Ferrocene,
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