amavadin- BASED VANADIUM COMPLEXES STRUCTURAL INVESTIGATIONS TON HUBREGTSE STRUCTURAL INVESTIGATIONS STRUCTURAL UITNODIGING VOOR HET BIJWONEN VAN DE OPENBARE VERDEDIGING VAN HET PROEFSCHRIFT OF EN DE STELLINGEN OP AMAVADIN-BASED VANADIUM COMPLEXES VANADIUM AMAVADIN-BASED DINSDAG 17 APRIL 2007 OM 12.30 UUR IN DE SENAATSZAAL ITNODIGING VAN DE TECHNISCHE UNIVERSITEIT DELFT U MEKELWEG 5 DELFT Voorafgaand aan de verdediging is er om 12.00 uur een toelichting voor niet-chemici. Na afloop van de plechtigheid bent u van harte welkom op de receptie in hetzelfde gebouw. Ton Hubregtse Anna Blamanlaan 8 2104 SE Heemstede 023-5283330 [email protected] T PARANIMFEN: . HUBREGTSE Huub Hubregtse [email protected] 06-46277320 Robert de Vries 2007 [email protected] belonging to the thesis ‘Structural investigations of amavadin-based vanadium complexes’ by Ton Hubregtse 1. Strongly acidic ion-exchange resins should not be used to purify molecules that rely on non-covalent bonds. E. M. Armstrong; D. Collison; N. Ertok; C. D. Garner, Talanta , 2000 , 53 , 75–87. H. Kneifel; E. Bayer, J. Am. Chem. Soc. , 1986 , 108 , 3075–3077. 2. The rule that states that the exception proves the rule is proven because there is no exception to this rule that can prove it. 3. The NMR data of Smith et al. can much better be explained when it is considered, given the three possible ligand stereoisomers and the two possible vanadium configurations, that six enantiomeric pairs of the [V( R,S-hidba) 2]-anion can be formed instead of three. P. D. Smith et al. , J. Chem. Soc., Dalton Trans. , 1997 , 4509–4516. 4. Fitness-equipment that does not make you tired and magical potions for improving your physical appearance are bestsellers because people expect to have bought the solution for their lack of discipline. 5. The determination of the number of water molecules in a sample by elemental analysis is not a reliable method. Chapter 5 of this thesis. 6. The term ‘conformational isomers’, used by Deutsch et al. for the indication of the reaction products of glycerol and benzaldehyde is incorrect. J. Deutsch; A. Martin; H. Lieske, Journal of Catalysis , 2007 , 245 , 428–435. 7. Without dreaming of the future one will never see opportunities. 8. The authors of the reported one-pot synthesis of acetic acid from methane and trifluoracetic acid (as CO-donor and solvent) should first consider the atom efficiency and the fluorinated by- products before comparing their synthesis with the industrial process. P. M. Reis et al. , Angew. Chem. Int. Ed. , 2003 , 42 , 821–823. 9. It can not be proven that the biological homochirality on Earth is of extraterrestrial origin. J. Bailey et al. , Science , 1998 , 281 , 672–674. 10. Speed skating is the only sport where one can become a world champion with two hands at the back. These propositions are considered opposable and defendable and as such have been approved by the supervisor, Prof. dr. R.A. Sheldon. behorende bij het proefschrift ‘Structural investigations of amavadin-based vanadium complexes’ van Ton Hubregtse 1. Sterk-zure ionenwisselaars zouden niet gebruikt moeten worden om moleculen te zuiveren die non-covalente bindingen hebben. E. M. Armstrong; D. Collison; N. Ertok; C. D. Garner, Talanta , 2000 , 53 , 75–87. H. Kneifel; E. Bayer, J. Am. Chem. Soc. , 1986 , 108 , 3075–3077. 2. De regel die zegt dat de uitzondering de regel bevestigt, wordt bevestigd doordat hij geen uitzondering kent die hem kan bevestigen. 3. De NMR-resultaten van Smith et al . zijn een stuk beter te verklaren als in ogenschouw wordt genomen dat er, gegeven de drie mogelijke ligandstereoisomeren en de twee mogelijke vanadiumconfiguraties, zes enantiomere paren van het [V( R,S-hidba) 2] anion kunnen ontstaan en geen drie. P. D. Smith et al. , J. Chem. Soc., Dalton Trans. , 1997 , 4509–4516. 4. Fitnessapparaten waarop je niet moe wordt en wondermiddeltjes voor een mooi uiterlijk verkopen zo goed omdat men verwacht de oplossing te hebben gekocht voor gebrek aan discipline. 5. Het bepalen van het aantal watermoleculen in een monster met behulp van elementanalyse is geen betrouwbare methode. Hoofdstuk 5 van dit proefschrift. 6. De term ‘conformational isomers’, gebruikt door Deutsch et al . ter aanduiding van de reactieproducten van glycerol en benzaldehyde is onjuist. J. Deutsch; A. Martin; H. Lieske, Journal of Catalysis , 2007 , 245 , 428–435. 7. Zonder dromen over de toekomst zul je nooit kansen zien. 8. De auteurs van de beschreven één-pots-synthese van azijnzuur uit methaan en trifluorazijnzuur (als CO-donor en oplosmiddel) zouden eerst de atoom-efficiëntie en de gefluoreerde bijproducten in beschouwing moeten nemen alvorens hun synthese met het industriële proces te vergelijken. P. M. Reis et al. , Angew. Chem. Int. Ed. , 2003 , 42 , 821–823. 9. Het is niet te bewijzen dat de biologische homochiraliteit op Aarde van buitenaardse oorsprong is. J. Bailey et al. , Science , 1998 , 281 , 672–674. 10. Hardrijden op de schaats is de enige sport waarbij je met twee handen op de rug wereldkampioen kunt worden. Deze stellingen worden opponeerbaar en verdedigbaar geacht en zijn als zodanig goedgekeurd door de promotor, Prof. dr. R.A. Sheldon. Structural investigations of amavadin-based vanadium complexes Cover design by Taeke Castelein (www.taekecastelein.nl) Structural investigations of amavadin-based vanadium complexes Proefschrift ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus prof. dr. ir. J.T. Fokkema, voorzitter van het College voor Promoties, in het openbaar te verdedigen op dinsdag 17 april 2007 om 12.30 uur door Teunis HUBREGTSE doctorandus in de scheikunde geboren te Winschoten Dit proefschrift is goedgekeurd door de promotor: Prof. dr. R. A. Sheldon Samenstelling promotiecomissie: Rector Magnificus voorzitter Prof. dr. R. A. Sheldon Technische Universiteit Delft, promotor Prof. dr. I. W. C. E. Arends Technische Universiteit Delft Dr. U. Hanefeld Technische Universiteit Delft Prof. dr. J. H. Teuben Rijksuniversiteit Groningen Prof. dr. R. Wever Universiteit van Amsterdam Prof. L. Pettersson Umeå Universitet, Zweden Dr. J. H. van Maarseveen Universiteit van Amsterdam Reservelid: Prof. dr. ir. H. van Bekkum Dr. U. Hanefeld en Prof. dr. I.W.C.E. Arends hebben als begeleiders in belangrijke mate aan de totstandkoming van dit proefschrift bijgedragen. The research described in this thesis was supported financially by the Dutch Ministry of Education, Culture and Sciences as part of the National Research School Combination Catalysis (NRSC-Catalysis). ISBN 978-90-9021780-2 Copyright © 2007 by Ton Hubregtse All rights reserved. No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording, broadcasting, or by any information storage and retrieval system, without permission in writing from the author. Printed by Gildeprint B.V., Enschede, The Netherlands Aan mijn vrouw Yvonne Aan mijn opa Ton Hubregtse (“grote Ton”) Die eerste inslag zal je maatstaaf zijn. Alle inslagen die volgen zul je eraan afmeten. Dirk Ayelt Kooiman Chapter 1 Introduction 9 Chapter 2 Enantioselective synthesis of the amavadin ligand and its 39 complexation of vanadium Chapter 3 Synthetic routes to amavadin-based ligands 51 Chapter 4 Complexation of vanadium by amavadin-based ligands 85 Chapter 5 Study of amavadin and oxidized amavadin in solution 113 Chapter 6 Amavadin-catalyzed (ep)oxidations 131 Chapter 7 Vanadium-catalyzed cyanide addition to aldehydes 149 Summary 161 Samenvatting 163 Dankwoord 165 Curriculum vitae 168 INTRODUCTION 1 1.1. History, occurrence and properties of vanadium 1.2. Vanadium in biological systems 1.3. Vanadium in homogeneous catalysis 1.4. Amavadin 1.5. Research objectives and outline of the thesis 1.6. References Chapter 1 1.1. History, occurrence and properties of vanadium Vanadium was originally discovered by the mineralogist Andrés Manuel del Río (1764–1849) in a mine in northern Mexico in 1801. [1,2] He believed that he had discovered the previously unknown element 23 in a sample of ‘brown lead’, now known as vanadinite (Pb 5(VO 4)3Cl). Because the colours of this mineral were reminiscent of those shown by chromium, he called the new element panchromium . He later renamed it erythronium (‘red’) as a reference to the red colour observed when the mineral was treated with acids. Unfortunately, he withdrew his claim when it was suggested by the French chemist Hippolyte-Victor Collet-Descotils (1773– 1815) that the mineral was only impure lead chromate. The element was ‘rediscovered’ in 1831 by the Swedish chemist Nils Gabriel Sefström (1787–1845) in remnants of iron ore at the Taberg mine in Sweden. He called the ‘new element’ vanadium , in honour of Vanadis, the Scandinavian goddess of love, beauty and youth. In the same year, Friedrich Wöhler (1800– 1882) came into possession of del Río's ‘brown lead’ and he established that the ‘new element’ of Sefström was identical to the one del Río had reported three decades earlier. Though, the name vanadium still stands rather than del Río's suggestion of erythronium. Metallic vanadium was not isolated until 1867 when Henry Enfield Roscoe (1833–1915) reduced vanadium chloride with hydrogen gas to give vanadium metal. He was also responsible for much of the early work on the element. Vanadium has been estimated to comprise about 136 ppm of the earth’s crustal rocks, in which it is the 19 th most abundant element and the fifth most abundant transition metal after iron, titanium, manganese and zirconium. Although vanadium is a common and widespread element, it is sparsely distributed; it is not mined as such but is generally obtained as a by- product of other ores and it is recovered from some crude oils, in particular those from Venezuela and Canada. The concentration of vanadium in the world’s oceans is about 20–35 nM, making it the second most abundant transition metal in the aquasphere.