Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2015 Solvento iron(IV) oxo complexes in catalytic oxidations and electron transfer reactions Hajem Bataineh Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Clinical Psychology Commons, and the Inorganic Chemistry Commons Recommended Citation Bataineh, Hajem, "Solvento iron(IV) oxo complexes in catalytic oxidations and electron transfer reactions" (2015). Graduate Theses and Dissertations. 14311. https://lib.dr.iastate.edu/etd/14311 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Solvento iron(IV) oxo complexes in catalytic oxidations and electron transfer reactions by Hajem Bataineh A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Inorganic Chemistry Program of Study Committee: Andreja Bakac, Co-Major Professor Aaron Sadow, Co-Major Professor William Jenks Javier Vela Keith Woo Iowa State University Ames, Iowa 2015 Copyright © Hajem Bataineh, 2015. All rights reserved. ii DEDICATION To my parents, brothers and sisters: Thank you for your endless support, encouragement and love. iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS ......................................................................................... v ABSTRACT ............................................................................................................... vi CHAPTER 1 GENERAL INTRODUCTION ......................................................... 1 Introduction .......................................................................................................... 1 Mononuclear nonheme iron-oxo complexes .................................................. 1 Reactivity of nonheme Fe(IV)-oxo complexes .............................................. 2 Factors affecting the reactivity of nonheme Fe(IV)-oxo complexes ............. 4 Aqueous iron(IV)-oxo complex ..................................................................... 6 Electron transfer properties of nonheme iron(IV)-oxo complexes ................ 7 Dissertation Organization .................................................................................... 10 References ............................................................................................................ 10 CHAPTER 2 pH-INDUCED MECHANISTIC CHANGEOVER FROM HYDROXYL RADICALS TO IRON(IV) IN THE FENTON REACTION ............ 14 Abstract …........................................................................................................... 14 Introduction .......................................................................................................... 15 Experimental ........................................................................................................ 16 Results .................................................................................................................. 17 Products and stoichiometry ............................................................................ 17 Kinetics of Fe(II)-H2O2 reaction at pH 6-7 .................................................... 22 Discussion ............................................................................................................ 27 Conclusions .......................................................................................................... 29 Acknowledgment ................................................................................................. 30 Supplemental Information (shown in Appendix A)............................................. 30 References ............................................................................................................ 30 CHAPTER 3 Fe(II) CATALYSIS IN OXIDATION OF HYDROCARBONS WITH OZONE IN ACETONITRILE ....................................................................... 33 Abstract …........................................................................................................... 33 Introduction .......................................................................................................... 34 Experimental ........................................................................................................ 35 Procedures ...................................................................................................... 36 Competition experiments ............................................................................... 37 Results .................................................................................................................. 38 Kinetics .......................................................................................................... 42 iv Effect of Fe(III), O 2 and water ....................................................................... 47 Competition experiments ............................................................................... 48 Discussion ............................................................................................................ 51 Conclusions .......................................................................................................... 56 Acknowledgment ................................................................................................. 57 Supplemental Information (shown in Appendix B) ............................................. 57 References ............................................................................................................ 57 CHAPTER 4 ELECTRON TRANSFER REACTIVITY OF AQUEOUS IRON(IV) OXO COMPLEX ..................................................................................... 60 Abstract ............................................................................................................... 60 Introduction .......................................................................................................... 61 Experimental ........................................................................................................ 63 Materials ........................................................................................................ 63 Procedures ...................................................................................................... 64 Results .................................................................................................................. 67 Polypyridyl complexes of Fe(II), Ru(II) and Os(II) ...................................... 67 Phenothiazines (CPZ and TFP) ...................................................................... 69 HABTS -.......................................................................................................... 70 Other substrates .............................................................................................. 70 Discussion ............................................................................................................ 74 Conclusions .......................................................................................................... 80 Acknowledgment ................................................................................................. 81 Supplemental Information (shown in Appendix C) ............................................. 81 References ............................................................................................................ 81 GENERAL CONCLUSIONS .................................................................................... 86 References ............................................................................................................ 88 APPENDIX A pH-INDUCED MECHANISTIC CHANGEOVER FROM HYDROXYL RADICALS TO IRON(IV) IN THE FENTON REACTION ............ 90 APPENDIX B Fe(II) CATALYSIS IN OXIDATION OF HYDROCARBONS WITH OZONE IN ACETONITRILE ....................................................................... 110 APPENDIX C ELECTRON TRANSFER REACTIVITY OF AQUEOUS IRON(IV) OXO COMPLEX ..................................................................................... 131 v ACKNOWLEDGMENTS I would like to thank my major professor, Dr. Andreja Bakac, for her guidance, encouragement, patience and friendship. I would also like to thank the other committee members for their comments and support. In addition, I would also like to thank my friends, colleagues, the chemistry department faculty and staff for making my time at Iowa State University a wonderful experience. I would especially like to thank my current and former fellow group members for their insightful discussions, and friendship. Finally, thanks to my family for their encouragement and support throughout my life. vi ABSTRACT Iron(IV)-oxo species are powerful oxidants that are involved as intermediates in iron- catalyzed oxidations of organic substrates. This includes their role in enzymatic oxidations which provided strong incentive to generate, characterize and explore the chemistry of novel Fe(IV) compounds from the perspective or reactivity and mechanism. The simplest iron(IV) complexes that have been prepared in solution are aqueous Fe(IV)-oxo ions. Even though these species can be conveniently generated from Fe(II) precursors