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University of Groningen Alkaline Earth Organometallic Compounds In University of Groningen Alkaline earth organometallic compounds in homogeneous catalysis Penafiel, Johanne IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2016 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Penafiel, J. (2016). Alkaline earth organometallic compounds in homogeneous catalysis: Synthesis, characterization and catalytic activity of calcium and magnesium complexes [Groningen]: Rijksuniversiteit Groningen Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 11-02-2018 Alkaline earth organometallic compounds in homogeneous catalysis Synthesis, characterization and catalytic activity of calcium and magnesium complexes Proefschrift ter verkrijging van de graad van doctor aan de Rijksuniversiteit Groningen op gezag van de rector magnificus prof. dr. E. Sterken en volgens besluit van het College voor Promoties. De openbare verdediging zal plaatsvinden op maandag 22 februari 2016 om 11.00 uur door Johanne Penafiel geboren op 16 september 1985 te San Isidro, Lima, Peru Promotor Prof. dr. S. Harder Beoordelingscommissie Prof. dr. A. J. Minnaard Prof. dr. J. G. de Vries Prof. dr. R. Dorta A ma famille, Catherine, Robert et Nicolas. The work described in this thesis was performed at the Stratingh Institute for Chemistry, University of Groningen, The Netherlands and at the Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg, Germany. The work was financially supported by the Dutch National Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis). Cover design : Catherine, Robert and Johanne Penafiel Printed by : Ipskamp Drukkers, Enschede, The Netherlands ISBN: 978-90-367-8499-3 (printed version) ISBN: 978-90-367-8498-6 (digital version) Contents The organometallic chemistry of alkaline earth metals ........................................................ 1 1.1 Alkaline earth metals ......................................................................................................................................... 2 1.1.1 The essentials ............................................................................................................................................... 2 1.1.2 Similarities between magnesium and zinc ..................................................................................................... 3 1.1.3 Grignard reagents ......................................................................................................................................... 4 1.1.4 The Schlenk equilibrium ................................................................................................................................ 5 1.2 Synthesis of alkaline earth metal organometallic compounds ........................................................................... 6 1.2.1 Post-Grignard reagents ................................................................................................................................. 6 1.2.2 Organoelimination ......................................................................................................................................... 6 1.2.3 Transamination.............................................................................................................................................. 7 1.2.4 Salt metathesis .............................................................................................................................................. 7 1.2.5 Direct metallation ........................................................................................................................................... 8 1.2.6 Redox transmetallation .................................................................................................................................. 8 1.2.7 Metal exchange ............................................................................................................................................. 9 1.3 Alkaline earth metal organometallic compounds in homogeneous catalysis ..................................................... 9 1.3.1 Hydroamination (C−N bond formation) ....................................................................................................... 10 1.3.2 Hydrophosphination (C−P bond formation) ................................................................................................. 11 1.3.3 Hydrosilylation (C−Si bond formation) ........................................................................................................ 12 1.3.4 Hydroboration (B−N and B−O bond formation) .......................................................................................... 12 1.3.5 Hydrogenation (C−H bond formation) ......................................................................................................... 12 1.3.6 Polymerization ............................................................................................................................................. 13 1.3.7 C−C bond formation and miscellaneous reactions ..................................................................................... 14 1.4 Outline of the thesis ......................................................................................................................................... 14 1.5 References ...................................................................................................................................................... 15 Alkaline earth metal complexes in asymmetric catalysis ..................................................21 2.1 Introduction ...................................................................................................................................................... 22 2.1.1 Chiral compounds ....................................................................................................................................... 22 2.1.2 Alkaline earth metals in asymmetric catalysis ............................................................................................. 24 2.1.3 Chiral ligands in asymmetric catalysis ......................................................................................................... 30 2.2 Aim of the project ............................................................................................................................................. 32 2.3 Results and discussion .................................................................................................................................... 33 2.3.1 Phosphoramidites ........................................................................................................................................ 33 2.3.2 Secondary Phosphine Oxides ..................................................................................................................... 40 2.4 Conclusions ..................................................................................................................................................... 44 2.5 Experimental section ....................................................................................................................................... 45 2.5.1 General ....................................................................................................................................................... 45 2.5.2 General procedure for complex synthesis ................................................................................................... 51 2.5.3 Intramolecular hydroamination of aminoalkenes ......................................................................................... 52 2.5.4 Single-crystal X-ray structure determination ................................................................................................ 52 2.6 References ...................................................................................................................................................... 53 Magnesium complexes in carbon dioxide activation .........................................................57 3.1 Introduction ...................................................................................................................................................... 58 3.1.1 Global warming and climate change ........................................................................................................... 58 3.1.2 Different strategies for CO2 transformation.................................................................................................. 58 3.1.3 Main group elements in CO2 activation ....................................................................................................... 59 3.1.4 FLP activation
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