N-HETEROCYCLIC CARBENE GOLD HYDROXIDE COMPLEXES AS BOND ACTIVATION REAGENTS Stéphanie Dupuy A Thesis Submitted for the Degree of PhD at the University of St Andrews 2014 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/10023/6613 This item is protected by original copyright N-Heterocyclic Carbene Gold Hydroxide Complexes as Bond Activation Reagents Stéphanie Dupuy This thesis is submitted in partial fulfilment for the degree of PhD at the University of St Andrews 18/08/2014 i Candidate’s declarations I, Stéphanie Dupuy, hereby certify that this thesis, which is approximately 65,000 words in length, has been written by me, and that it is the record of work carried out by me, or principally by myself in collaboration with others as acknowledged, and that it has not been submitted in any previous application for a higher degree. I was admitted as a research student in September 2010 and as a candidate for the degree of PhD in September 2011; the higher study for which this is a record was carried out in the University of St Andrews between 2010 and 2014. Date …………….. signature of candidate ………………. ii iii Supervisor’s declaration 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 …………….. signature of supervisor ………………. iv v Permission for publication In submitting this thesis to the University of St Andrews 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 publication of this thesis: -Access to printed copy and electronic publication of this thesis through the University of St Andrews. Date ……………… signature of candidate ………………. signature of supervisor ……………… vi vii Dedicated to my grandfather Dediée à mon grand-père “Survivre à une souffrance intolérable, c’est tolérer l’intolérable” Robert Sabatier viii ix Acknowledgments These past 4 years as PhD student have been quite a journey. I have learnt a lot and owe a great deal of thanks to many people that supported me during this time and made me become a better, grown and mature person. First and foremost I want to give a wide thank to all the people that have come to my life over these years and that have made me the person that I am today. I would have certainly not make it until the end of this adventure without you. I would like to thank Prof. Steven P. Nolan for giving me the opportunity to do my doctoral studies in his research group. You have always pushed me to achieve things and I won’t hide that it has been hard and painful sometimes but that at the end I must reckon that it has always made me outdo myself and got the best out of me. Thank you also for the huge freedom that you gave me in the lab and that allowed me to enrich greatly my knowledge. Now comes the time to thank some outstanding postdocs that came by in our group and never said no to a young graduate that was seeking advice, explanations or when, at the end bombarding them with chapter reading. In particular, Dr Anthony Chartoire (Beaaaavverrr) and Dr Anthony Martin (Rrrrrouuu rrrrououu Pidgeon) that have made our lab a fantastic place to work in with their everyday animal jokes that always brought a big laugh to me even in bad days. You have both provided me with lots of guidance and tried hard to insert some knowledge into my stubborn head and I am forever grateful. Beaver thank you also for not getting tired to listen to my eternal “I’m jinxed anyway I should stop chemistry and do pizza deliveries”. A huge thank to Dr David Nelson or “Jacques Cousteau” or “Fluffy Pony” for your everyday good mood, your invaluable time in explaining things, your patience and your caring as well as unforgettable moment during our organometallic seminars. You are a true great chemist (“Parlez-vous le Francais? Ehmmm no”). I would like to thank the past and current members of the lab that I had the privilege to meet for their support, encouragement and that have made our work area an amazing place to work in. Special thank to Dr Pierrick Nun who supervised me when I arrived and succeeded in coping with my stubbornness, Dr Jose Fernandez Salas (Pepito), Dr Sebastien Meires (my workalcoholic night colleague), Dr Fady Nahra (thanks for the countless dancing time attempts in and outside the lab!), Frederic Izquierdo (Maurrrrrriiiice, thanks for the food rationing during these last two years). Thanks a lot guys! During those 4 years, I have met countless people and some of them have come to be very close friends. I wish to thank first Adrian Gomez-Suarez for being a great colleague to work with, his everyday good mood, his Spanish personality that will leave me some very good memories. I could always count on you during those 4 years and I want tot thank you for that x Acknowledgments (and obviously as well for not getting desperate with my incapacity to handle computer software). Next, a great praise to another “Spaniard”: my tiny partner Dr Alba Collado-Martinez or Mlle petit penguin. You have become one of my closest friends here. I will never forget your continued support in driving me to be a better chemist and person, your guidance and listening. I would not have got out of this thesis in one piece without you la signorita pinguinita. You have been the shoulder I needed toward the end of that PhD. My sanity is intact thanks to you. Thank you for sharing not only your knowledge but your healthy way of living, your organization and trying to pass them to me (even of it seems I am a hopeless cause...). You have taken so much care and become a surrogate “mommy” to me. You especially deserve credit for putting up with me at bad days and some nights out (“I love mojitos”). For just being you, thank you. You are so tiny ☺ To not only one of our best lab technician but also a personal friend, I want to thank Julie Mayen. Ma poule, merci d’être venue et revenue en Ecosse. Tu fais partie des gens qui m’ont donné la force de finir cette thèse et qui m’ont soutenu le plus. Je n’y serais jamais arrivée sans toi. Ne perds jamais cette bonne humeur et positive attitude qui te definissent, they are golden. Je garde a tout jamais avec moi ton fameux dicton “Ca va aller”. Garde moi une petite place sur ton canap’ a Nice! To my family, thank you for your support during all these years and always believing in me. I could never repay all you have done for me. Thank you for your love. Last but not least, I would like to express my deepest gratitude to my best friend Aurore. We have come a long way since we met 20 years ago and though we lost track of sight of each other for some years, we finally reunited again and I’m thankful for that everyday. It is even too difficult to find words to express my gratefulness to you. You are my rock and my shoulder. Your strength and your faith in me has always encouraged and motivated me to advance further and not give up. You are my family and no matter the distance or twist in our lives I will never again let our friendship get lost. A final thank to my fellow 4-year PhD colleagues Simone Manzini, Scott Patrick, Byron Truscott and Adrian Gomez-Suarez. It has been a long road since we all started together 4 years ago. We have matured, laughed and suffered altogether and we could always count on each other. You are amazing people and I am glad to have shared this journey with you guys. We did it! xi Author Contributions The majority of the work reported in this thesis has been published as peer-reviewed journal articles as described below. Unless stated otherwise, the work reported is all my own work and I was the primary researcher on all projects and prepared all published manuscripts: Chapter 2: - Adapted with permission from “The Role of Metal Hydroxide Complexes in Late Transition Metal-Mediated Transmetalation Reaction: The Case of Gold”, Dupuy, S.; Crawford, L.; Bühl, M.; Slawin, A. M. Z.; Nolan, S. P., Adv. Synth. Catal. 2012, 354, 2380.