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STUDIES IN PHOSPHORUS-SELENIUM CHEMISTRY Jacqueline Garland A Thesis Submitted for the Degree of PhD at the University of St Andrews 2013 Full metadata for this item is available in Research@StAndrews:FullText at: http://research-repository.st-andrews.ac.uk/ Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/3688 This item is protected by original copyright Studies in Phosphorus-Selenium Chemistry Jacqueline Garland This thesis is submitted in partial fulfilment for the degree of Doctor of Philosophy (PhD.) at the University of St Andrews and Doctor rerum naturalium (Dr. rer. nat.) at the Universität Leipzig 21st February 2013 Supervisors: Prof. J. D. Woollins Prof. E Hey-Hawkins Declarations I, Jacqueline Garland, hereby certify that this thesis, which is approximately 53000 words in length, has been written by me, that it is the record of work carried out by me and that it has not been submitted in any previous application for a higher degree. I was admitted as a research student in September, 2008 and as a candidate for the degree of July 2009; in the higher study for which this is a record was carried out in the University of St Andrews and the Universität Leipzig between 2008 and 2013. Date: 21st February 2013 Signature of candidate: I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of PhD. in the University of St Andrews and that the candidate is qualified to submit this thesis in application for that degree. Date: 21st February 2013 Signature of supervisor: I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of Dr. rer. nat. in the Universität Leipzig and that the candidate is qualified to submit this thesis in application for that degree. Date: 21st February 2013 Signature of supervisor: 1 In submitting this thesis to the University of St Andrews and the Universität Leipzig I understand that I am giving permission for it to be made available for use in accordance with the regulations of the University Library for the time being in force, subject to any copyright vested in the work not being affected thereby. I also understand that the title and the abstract will be published, and that a copy of the work may be made and supplied to any bona fide library or research worker, that my thesis will be electronically accessible for personal or research use unless exempt by award of an embargo as requested below, and that the library has the right to migrate my thesis into new electronic forms as required to ensure continued access to the thesis. I have obtained any third-party copyright permissions that may be required in order to allow such access and migration, or have requested the appropriate embargo below. The following is an agreed request by candidate and supervisor regarding the electronic publication of this thesis: (i) Access to printed copy and electronic publication of thesis through the University of St Andrews and the Universität Leipzig. Date: 21st February 2013 Signature of candidate: Date: 21st February 2013 Signature of supervisor: Date: 21st February 2013 Signature of supervisor: 2 Acknowledgements First and foremost, I would like thank Derek, without whom I would be half the chemist I am today. Thank you for believing in me, supporting me and giving me the odd nudge when I needed it. Thanks also must go to Alex, who has offered endless support and natters, just as I thought I was going mad. Many thanks go to Prof. Hey- Hawkins, for her help and guidance on the project and for giving me the opportunity to work in her laboratories. Without the help of the technicians and other academic staff in analysis, none of this work would have been characterised. Many thanks therefore are needed to go to Tomas and Melanja in NMR (extra thanks to Tomas for putting up with my less than intelligent questions), Caroline Horsburgh in MS, Stephen Boyer at London Met for the experimental analyses and a massive thanks to Alex and Team Crystallography, for all their work on solving my ‘I made something’ efforts. Here I must also mention Bobby Cathcart for his unending banter and all those in the workshops, stores and offices. I must also thank the conglomerate for an enjoyable experience both in the lab and in the pub. I am indebted to Dr. Ken Armstrong and Matt Ray for teaching me the rules of football, Dr. Brian Morton for teaching me the rules of fashion and Dr. Paul Waddell for filling in the vast gaps between. Special thanks go to Fergus and Lynzi for reading and correcting my book and their diplomacy for never once saying it was dull. Becca, Lucy and Marie, my Mafia, I thank for their support and love, as well as destroying my house and my sleep patterns and of course Fergus for employing us all. I thank Conor for the countless cups of tea, Kasun, Joy and Paula for being the shiny, happy and smily people that they are and Surge for the banter. A big shout out must go to the UEA gang, without whom I would have gone mental in the final six months. Dr. Mould: We did it. To my girlies: Alex, Dani, Ini, Lynzi, Sarah and Zoe thank you for putting up with my moaning, stress and tears, but also giving me the love and support that I need. Thanks for reminding me that I am both not as clever as I make out to be and yet also smarter than I think I am. I feel I must also give a special mention to gin here, and his girlfriend tonic, without whom I would be more well off, but a lot more stressed. 3 Ich möchte mich bei Dr. Sebastian Bauer, Dr. Carolin Limburg, Dr. Steffen Tschirschwitz und Dr. Matthias Scholz bedanken für ihre Hilfe, Unterstützung und all ihre Ratschläge im Labor. Ich habe eine wunderschöne Zeit in den Leipziger Laboren gehabt und ihre Weisheit war nicht zu toppen! Zunächst möchte ich mich bei all denjenigen im AK H2 bedanken, insbesondere Ivana, Julian, Tobi, Paul und Susi die mich während der Promotion unterstützt haben. Ein besonderen dank gilt an Tobi und Sebastian für das Korrekturlesen. Mein Dank gilt auch an Dr. Peter Lönnecke für die Messung und Lösung der Kristallstrukturen, Frau Zäbe für die zahlreiche NMR-Messungen, Frau Scholz für die Aufnahme der IR‐Spektren, sowie Fr. Oehme für die Aufnahme der Massenspektren und den Herren Eckert und Fatum für die Anfertigung und Reparatur von Glasgeräten. An Frau Aust: Danke danke danke, für all die Unterstützung, Liebe und Hilfe die du mir immer gegeben hast als ich sie brauchte. An mein kleines Brüderchen: *That face*. An Jule, Steffen, Anna, Basti und Nicole, Team Arschtritt: ich hätte es nie geschafft ohne eure Unterstützung. Tausend mal dank! An die Herren Groß, Eschberger, Hirschfeld und Geigenmüller, Team Gin: stellt mal den Hendrick’s kalt und bereitet schonmal das Boot vor, ich bin gleich wieder da. An den Chemie-, Ba-Hu- und mittlerweile auch Medielferrat, sowie alle Leiziger Studentenclubs: Ihr seid die Besten. Vielen lieben dank für die Erinnerungen, den Spass sowie den Schwachsinn, der dazu gehört hat, Mitglied im Elferrat zu sein. Es war mir eine Ehre, bleibt so wie ihr seid und behaltet eure Narrheit. To Mum, Dad, my Maffew and the rest of the supporting cast I call my family: Thanks to all of you for being there and doing what you do best: Picking me up when I’m down and helping me see the lighter side of life. Without you guys I would be lost!! Oh and thanks to Skimble for ‘writing’ the whole thing for me/with me. One final question though… Chemiker, wo seid ihr? 4 Abstract Phosphorus-Selenium chemistry has seen a surge in development over the last five to ten years thanks to the optimisation of the synthesis of 2,4-diphenyl-1,3,2,4- diselenadiphosphetane-2,4-diselenide, Woollins’ Reagent. This selenium analogue of the well known Lawesson’s Reagent has proved itself to be a valuable asset to modern inorganic chemistry, providing a route to novel heterocycles, as well as acting as a selenation reagent with a wide range of functional groups. A series of new ammonium phenylphosphonamidodiselenoate ligands were synthesised via the reaction of Woollins’ Reagent with a range of amines. The products were obtained in high yields and could be used as ligands for the synthesis of novel metal complexes. The reaction of diisopropylamine N-isopropyl-P- phenylphosphonamidodiselenoate with nickel(II) acetate produces a dimeric structure, whilst the reaction with copper(II) acetate yields a beautiful cluster of the form Cu6Se3L6. The phenylphosphonamidodiselenoate ligands were further reacted with a range of cis-Pt(PR3)2Cl2 complexes to form a library of 20 novel compounds, which were studied by 31P{1H}, 77Se{1H} and 195Pt{1H} NMR spectroscopy. The X-ray crystal structure of one of these compounds was obtained, which confirmed the atom connectivity and spatial arrangement of the complexes and the geometry around the platinum centre. During investigations into the above-mentioned platinum complexes, it was postulated that an increase in steric bulk of the phosphine ligands would aid crystallisation of the products. As such, trimesityl-, dimesitylphenyl- and mesityldiphenyl phosphine were synthesised and reacted with elemental sulfur and selenium and hydrogen peroxide, as well as Pt(cod)Cl2 and K2[PtCl4], yielding nine new structures, all of which were characterised by X-ray crystallography, 31P{1H}, 13C{1H} and 1H NMR spectroscopy.
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