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Cyclometalation of Phosphinines Via C-H Activation : Towards Functional Coordination Compounds

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Cyclometalation of Phosphinines Via C-H Activation : Towards Functional Coordination Compounds Cyclometalation of phosphinines via C-H activation : towards functional coordination compounds Citation for published version (APA): Broeckx, L. E. E. (2013). Cyclometalation of phosphinines via C-H activation : towards functional coordination compounds. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR760622 DOI: 10.6100/IR760622 Document status and date: Published: 04/12/2013 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. 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If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 09. Oct. 2021 Cyclometalation of Phosphinines via C-H Activation Towards Functional Coordination Compounds PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de rector magnificus prof.dr.ir. C.J. van Duijn, voor een commissie aangewezen door het College voor Promoties, in het openbaar te verdedigen op woensdag 4 december 2013 om 16:00 uur door Leen Elisabeth Emiel Broeckx geboren te Mol, België Dit proefschrift is goedgekeurd door de promotoren en de samenstelling van de promotiecommissie is als volgt: voorzitter: prof.dr.ir. J.C. Schouten 1e promotor: prof.dr. C. Müller 2e promotor: prof.dr. D. Vogt leden: prof.dr. M. Hissler (Université de Rennes1) dr. A. Macchioni (Università di Perugia) prof.dr. K. Lammertsma (Vrije Universiteit Amsterdam) prof.dr. B.J.M. Klein Gebbink (Universiteit Utrecht) prof.dr.ir. R.A.J. Janssen (TU/e) “When you make a choice, you change the future.” Deepak Chopra “Cyclometalation of Phosphinines via C-H Activation: Towards Functional Coordination Compounds” A catalogue record is available from the Eindhoven University of Technology Library ISBN: 978-90-386-3491-3 This research was sponsored by a Vidi grant with project number 700.58.424 of the Netherlands Organization for Scientific Research (NWO), as well as the European Cooperation in Science and Technology (COST) Action CM0802 (PhoSciNet), and a Van Gogh grant from the French-Dutch academy. Coverontwerp: Yoran Zonneveld en Leen E. E. Broeckx Druk: TU/e PrintService Copyright © 2013 by Leen E. E. Broeckx Table of Contents Chapter 1 Cyclometalation via C-H Activation of 2-Arylphosphinine Derivatives: Towards Functional Coordination Compounds ....................................................................................... 1 1.1 Introduction .............................................................................................................................. 2 1.2 Tuning the Coordination and Cyclization Step................................................................... 3 1.3 Mechanism of Cyclometalation via C-H Activation ........................................................... 5 1.3.1. Cyclometalation via Oxidative Addition ............................................................... 5 1.3.2. Electrophilic Metalation-Deprotonation ................................................................ 6 1.3.3. Agostic Interactions................................................................................................... 7 1.4 Application of Cyclometalated Products ............................................................................. 8 1.4.1. Water Oxidation Catalysts ....................................................................................... 8 1.4.2. Phosphorescent Transition Metal Complexes in OLEDs ................................... 11 1.5 Phosphinines .......................................................................................................................... 14 1.6 Scope of Phosphinine Cyclometalation .............................................................................. 18 1.7 References ............................................................................................................................... 19 Chapter 2 Unprecedented Formation of 2,4,6-Triphenylphosphinine-Based Cyclometalated Ir(III) and Rh(III) Complexes via C-H Bond Activation .................................................................. 23 2.1 Introduction ............................................................................................................................ 24 2.2 Cyclometalated Iridium and Rhodium Complexes Based on Phosphinine .................. 25 2.3 Reactivity Study of Phosphinine-M(III) Complexes ......................................................... 31 2.3.1. Influence of NaOAc as Base ................................................................................... 31 2.3.2. Reactivity of the P=C Double Bond Towards Nucleophilic Attack .................. 33 2.4 Application of 2,4,6-Triphenylpyridine in the Cyclometalation Reaction .................... 41 2.5 Conclusions ............................................................................................................................ 43 2.6 Experimental Section ............................................................................................................. 44 2.7 References ............................................................................................................................... 50 i Table of Contents Chapter 3 Cyclometalation of Aryl Substituted Phosphinines: a Mechanistic and Kinetic Investigation ................................................................................................................................. 53 3.1 Introduction ........................................................................................................................... 54 3.2 Synthesis and Characterization of 2,4,6-Triarylsubstituted Phosphinines ................... 55 3.3 C-H Activation of Substituted 2,4,6-Triarylphosphinines ............................................... 58 3.3.1. Structural Characterization of Cyclometalated Complexes Based on Symmetrically Substituted Phosphinines ........................................................... 59 3.3.2. Structural Characterization of Cyclometalated Complexes Based on Non-Symmetrically Substituted Phosphinines .................................................. 61 3.4 Rate of Cyclometalation of Functionalized 2,4,6-Triarylphosphinines ......................... 63 3.4.1. Symmetrically Substituted Phosphinines ............................................................ 63 3.4.2. Non-Symmetrically Substituted Phosphinines ................................................... 67 3.5 Regioselectivity of the Cyclometalation Reaction ............................................................ 69 3.6 Cyclometalation of 2,4,6-Triarylphosphinines: Mechanistic Investigation ................... 73 3.7 Kinetic Investigation and Kinetic Isotope Effect of the Cyclometalation ...................... 75 3.8 Conclusions and Outlook ..................................................................................................... 79 3.9 Experimental Section ............................................................................................................ 81 3.10 References ............................................................................................................................. 96 Chapter 4 Reactivity Study of Cyclometalated Phosphinine-Ir(III) Complexes: Towards Novel Water Oxidation Catalysts ......................................................................................................... 99 4.1 Introduction ......................................................................................................................... 100 4.2 Preparation of Cationic Cyclometalated Phosphinine-Ir(III) Complexes ................... 102 4.2.1. Synthetic Study Towards Ligand Exchange ..................................................... 102 4.2.2. Crystallographic Characterization of Cationic Ir(III) Complexes .................. 104 4.3 Reactivity of Cationic Ir(III) Complex Towards Water Addition ................................. 106 4.4 Application of Phosphinine-Based Water Oxidation Catalysts ...................................
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