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Synthesis and Coordination Chemistry of Multidentate Phosphine Ligands

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Synthesis and Coordination Chemistry of Multidentate Phosphine Ligands Synthesis and Coordination Chemistry of Multidentate Phosphine Ligands Mark Peter Driver A thesis submitted to Cardiff University in candidature for the degree of Doctor of Philosophy Department of Chemistry, Cardiff University September 2016 Declaration This work has not been submitted in substance for any other degree or award at this or any other university or place of learning, nor is being submitted concurrently in candidature for any degree or other award. Signed …………………………………………….……(candidate) Date ………………….……. STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree of PhD Signed …………………………………………….……(candidate) Date ………………….……. STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated, and the thesis has not been edited by a third party beyond what is permitted by Cardiff University’s Policy on the Use of Third Party Editors by Research Degree Students. Other sources are acknowledged by explicit references. The views expressed are my own. Signed …………………………………………….……(candidate) Date ………………….……. STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loan, and for the title and summary to be made available to outside organisations. Signed …………………………………………….……(candidate) Date ………………….……. STATEMENT 4: PREVIOUSLY APPROVED BAR ON ACCESS I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loans after expiry of a bar on access previously approved by the Academic Standards & Quality Committee. Signed …………………………………………….……(candidate) Date ………………….……. i Abstract The work presented herein is concerned with the design, synthesis and characterisation of novel phosphorus containing ligands and the metal complexes thereof. Chapter 1 will provide an introduction to the field and present an overview of recent developments in the literature. Chapter 2 deals with the development of a synthetic route towards triphosphine macrocycles. The synthesis of bis(2-(phosphino)ethyl)phosphines is presented and their coordination chemistry with first row transition metals (Cr, Fe, Ni, Cu) is described. The ability of these complexes to act as templates in the formation of macrocyclic ligands is assessed. Chapter 3 explores the synthesis of novel chiral multidentate phosphine ligands derived from glycidyl phosphine synthons. The reaction of diphenylglycidyl phosphine with P, N and S based nucleophiles results in the rapid construction of chiral heterodonor ligand frameworks. Preliminary studies of the reactivity of these ligands with metal centres will be presented. Chapter 4 investigates the synthesis of chiral-at-aluminium complexes based upon a novel γ-amino-β-hydroxyphosphine oxide ligand. Two discreet aluminium alkyl complexes were identified and the interconversion of these species was studied by spectroscopic and computational means. Chapter 5 concerns the coordination chemistry of bicyclic multidentate ER-NHCs with Pd(0), Pt(0) and Au(I) metal centres. The M(0) complexes display an unexpected proclivity towards the κ1-C coordination mode. This further informs the discussion of the factors controlling the variable coordination chemistry of such ligands in the design of novel catalytic systems. ii Acknowledgments I am very grateful to my supervisors Professor Peter G. Edwards for giving me this opportunity and to Dr Ian Fallis for your continued advice and guidance. Thanks must also be given to Dr Paul Newman; your support and friendship have been invaluable to me, I would never have achieved this without your help. I give thanks also to Dr Ben Ward for your advice and assistance with DFT calculations. My gratitudes are also due to all of the professional services staff at Cardiff University; especially Dr Rob Jenkins, Robin Hicks, Simon Waller, Tom Williams, Jamie Cross, Simon James and Gaz Coleman. This work would not have been possible without your hard work, dedication and professionalism. To all the members of the Edwards group, particularly Mauro, Brendan, Lenali and Tom, Thank you for everything. I’d also like to mention the students who have helped immensely in the production of this work, Axel, Owain and Jamie. On a personal note, I am eternally indebted to my family for their unfailing support throughout everything I do. You give me the strength and encouragement to achieve my dreams. I have been lucky enough to make many wonderful friends (and one “powerful enemy”) during my time in Cardiff. My best memories and experiences of the last few years are of times spent with you. I can’t thank you all enough for your support and friendship. To everyone else who has contributed in so many ways, thank you. iii Contents Declaration ................................................................................................................................ i Abstract .................................................................................................................................... ii Acknowledgments ................................................................................................................... iii Contents .................................................................................................................................. iv List of Abbreviations ............................................................................................................... xi Chapter 1 – Introduction .......................................................................................................... 1 Phosphorus(III) ligands: An overview................................................................................... 2 Properties of phosphines ..................................................................................................... 3 Chemical properties ......................................................................................................... 3 Electronic properties ........................................................................................................ 4 Steric properties ............................................................................................................... 5 Structural features of primary and secondary phosphines ................................................. 7 Multidentate ligands ............................................................................................................ 8 Synthesis of phosphine ligands .......................................................................................... 10 Macrocyclic effect .............................................................................................................. 12 The origins of the macrocyclic effect ............................................................................. 13 Macrocyclic ligands ........................................................................................................ 14 Macrocycle synthesis ..................................................................................................... 17 Reactivity of macrocyclic phosphine complexes ........................................................... 25 iv Aims ................................................................................................................................... 29 References ......................................................................................................................... 30 Chapter 2 – Towards the synthesis of macrocyclic phosphines ............................................ 37 Aims of chapter 2 ............................................................................................................... 38 Ligand design and methodology .................................................................................... 38 Results and Discussion ....................................................................................................... 40 Ligand synthesis ............................................................................................................. 40 Cyclisation reactions with ‘hard’ metal templates ........................................................ 42 Fe piano stool complexes ............................................................................................... 45 Coordination chemistry of tertbutylbis(2-phenylphosphinoethyl)phosphine ............... 48 Conclusion .......................................................................................................................... 60 Experimental ...................................................................................................................... 61 General considerations .................................................................................................. 61 DFT calculations ............................................................................................................. 62 Synthesis of tertbutylbis(2–(diphenylphosphino)ethyl)phosphine, 1tBu ........................ 62 Synthesis of tertbutylbis(2–(phenylphosphino)ethyl)phosphine, 3tBu ........................... 62 Synthesis of phenylbis(2–(phenylphosphino)ethyl)phosphine, 3Ph ............................... 63 General synthesis of Fe piano stool complexes ............................................................. 63 Synthesis of trichloro tertbutylbis(2–(phenylphosphino)ethyl)phosphine chromium(III), 4 ....................................................................................................................................
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