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An Innovative Method to Generate Iodine(V and III)-Fluorine Bonds and Contributions to the Reactivity of Fluoroorganoiodine(III) Fluorides and Related Compounds

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An Innovative Method to Generate Iodine(V and III)-Fluorine Bonds and Contributions to the Reactivity of Fluoroorganoiodine(III) Fluorides and Related Compounds An Innovative Method to Generate Iodine(V and III)-Fluorine Bonds and Contributions to the Reactivity of Fluoroorganoiodine(III) Fluorides and Related Compounds Vom Fachbereich Chemie der Universität Duisburg-Essen zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation von Anwar Abo-Amer aus Irbid / Jordanien Referent: Prof. Dr. H.-J. Frohn Korreferent: Prof. Dr. G. Geismar Tag der mündlichen Prüfung: 26.01.2005 Die experimentellen Arbeiten wurden in der Zeit von Juli 2001 bis April 2004 unter Anleitung von Herrn Prof. Dr. H.-J. Frohn im Fach Anorganische Chemie des Fachbereiches Chemie am Campus Duisburg der Universität Duisburg-Essen durchgeführt. ACKNOWLEDGMENTS I would like to thank my supervisor Prof. Dr. Hermann-Josef Frohn (Distinguished Professor Inorganic Chemistry), for his guidance, encouragement, support throughout my graduate study, his willingness to share his technical knowledge and for having patience with me. He acted as the driving force behind this research. He provided his knowledge and expertise. He spent many time for constructive discussion, which enriched my knowledge, skill and my experience. I sincerely thank Prof. Dr. G. Geismar, the Korreferent, for his encouragement, support and constructive discussion. Also, I’m very grateful to Prof. Dr. Vadim Bardin for many fruitful discussions concerning topics in fluorine and boron chemistry. I have to thank my colleague Dr. Nicolay Adonin for helpful discussions. He provided not only scientific, but also moral support, and most of all friendship, throughout my study and research. I am also grateful to many other persons and I would like to acknowledge their significant contributions to my study: - Karsten Koppe, who has provided me with constant support, kind guidance and significant contribution, not only on my academic life but also on my personal life. - Wassef Al Sekhaneh, who inspired my research with his incredible knowledge. - Dietmar Jansen, Petra Fritzen, Christoph Steinberg, Andre´ Wenda, and Oliver Brehm, which all inspired my research with their incredible knowledge and helped for a warm and supportive environment. Special thanks are given to many faculty and staff members of the chemistry department (Duisburg-Essen Universität) for their assistance during my graduate study. In particular, thanks are pressed to Dr. Ulrich Flörke for the X-Ray crystallographic work. Special thanks to Mrs. Beate Römer and Mr. Manfred Zähres for NMR spectrometric measurements. My utmost appreciation and thanks are given to my wife, Eman Abu-Jadoua, for her love and support throughout my graduate career. I also thank my daughter, Mimas, and my son, Yamen, for bringing so much joy the moment they joined into my life in Germany. I warmly thank my parents, brothers and sisters for continuous inspiration and encouragement. The support of many friends through out my research (Prof. Dr. Alaa Hassan, Prof. Dr. Mohammad Shabat) has also been much appreciated. “After great pain, a formal feeling comes” Emily Dickinson Dedicated to… My Daughter Mimas, My Son Yamen, My Wife Eman, My Mother and Father Table of Contents I Table of Contents 1 Introduction 1 1.1 Bonding and Structure in Polyvalent Iodine Compounds 1 1.2 (Difluoroiodo)arenes 4 1.3 (Tetrafluoroiodo)arenes and (Difluorooxoiodo)arenes 6 1.3.1 (Tetrafluoroiodo)arenes 6 1.3.2 (Difluorooxoiodo)arenes 7 1.4 Iodine Pentafluoride 7 1.5 Iodonium Salts 9 1.5.1 Diaryliodonium Salts 9 1.5.2 Alkenyl(aryl)iodonium Salts 12 2 Objectives 14 2.1 Preparative Aspects 14 2.1.1 Iodine Pentafluoride 14 2.1.2 (Tetrafluoroiodo)arenes 15 2.1.3 (Difluorooxoiodo)arenes 15 2.1.4 (Difluoroiodo)arenes 15 2.1.5 Iodonium Salts 16 2.2 Reactivity, Structure, and Spectroscopy 17 3 Results and Discussion 19 3.1 Preparation of Iodine Pentafluoride (IF5) by a New Methodological Approach 19 3.1.1 Introduction 19 3.1.2 Relevant Reactivities of I(V)-F and I(V)-O Bonds 19 3.1.3 The Reaction of I(V)-O Compounds with aHF in a Two Phase System 20 3.1.4 The Important Steps in the Preparation of IF5 20 3.1.5 The Influence of the HF Concentration on the IF5 Formation 21 Table of Contents II 3.2 4-Fluoro-1-(tetrafluoroiodo)benzene by Oxygen-Fluorine Substitution 23 3.3 4-Fluoro-1-(difluorooxoiodo)benzene (p-C6H4FIOF2) by Treat- ment of 4-Fluoro-iodylbenzene with Hydrofluoric Acid 24 3.4 (Difluoroiodo)arenes (ArIF2) by Oxygen-Fluorine Substitution on ArIO with Hydrofluoric Acid as Reagent 25 The Influence of the HF Concentration on the Formation of (Difluoroiodo)arenes (ArIF2) 26 3.5 A Convenient Route to (Difluoroiodo)benzenes (ArIF2) Directly from (Diacetoxyiodo)benzenes 28 3.6 Iodonium Salts 30 3.6.1 The Synthesis of Diaryliodonium Salts Starting from (Difluoroiodo)arenes 30 3.6.2 The Synthesis of Alkenyl(aryl)iodonium Salts Starting from (Difluoroiodo)arenes 31 3.6.2.1 trans-1,2,3,3,3-Pentafluoroprop-1-enyl(fluorophenyl)iodonium Tetrafluoroborates 31 3.6.2.2 trans-1,2,3,3,3-Pentafluoroprop-1-enyl(pentafluorophenyl)iodonium Tetrafluoroborate 33 3.6.2.3 Preparation of Trifluorovinyl(fluorophenyl)iodonium Tetrafluoroborates 33 3.6.2.4 Preparation of Trifluorovinyl(pentafluorophenyl)iodonium Tetrafluoroborate 34 3.7 Selected Reactivities of Fluoro(difluoroiodo)benzenes C6H4FIF2 35 3.7.1 Reactivities with Nucleophiles and Lewis Bases 35 3.7.1.1 The Reaction of p-C6H4FIF2 with Trimethylsilylacetate 35 3.7.1.2 The Interaction of ArIF2 with 2,2´-Bipyridine 36 3.7.1.3 The Interaction of ArIF2 with (C6H5)3PO 37 3.7.1.4 The Reaction of ArIF2 with [NMe4]F 37 Table of Contents III 3.7.1.4.1 The Reaction of p-C6H4FIF2 with [N(CH3)4]F (1 : 1) in Dichloromethane 38 3.7.1.4.2 The 1 : 2 Reaction of p-C6H4FIF2 with [N(CH3)4]F in Dichloromethane 40 3.7.1.4.3 The 1 : 0.5 Reaction of p-C6H4FIF2 with [N(CH3)4]F in Dichloromethane 41 3.7.1.4.4 The Reaction of p-C6H4FIF2 with [N(CH3)4]F (1 : 1) in Acetonitrile 41 3.7.1.4.5 The Reaction of p-C6H4FIF2 with [N(CH3)4]F (1 : 3) in Dichloromethane 42 3.7.1.4.6 The 1 : 2 Reaction of o-C6H4FIF2 with [N(CH3)4]F in Dichloromethane 42 3.7.1.4.7 The 1 : 2 Reaction of m-C6H4FIF2 with [N(CH3)4]F in Dichloromethane 43 3.7.1.5 The Reaction of p-C6H4FIF2 with CsF 44 3.7.1.5.1 The Reaction of p-C6H4FIF2 with CsF (1 : 1) in Acetonitrile 44 3.7.1.5.2 The Reaction of p-C6H4FIF2 with CsF (1 : 2) in Acetonitrile 45 3.7.2 Reactions of C6H4FIF2 with Lewis and Brønsted Acids 46 3.7.2.1 The Reaction of p-C6H4FIF2 with C6H5PF4 46 3.7.2.2 The Reactions of p-C6H4FIF2 with Alcohols (MeOH, EtOH, CF3CH2OH) 47 3.7.2.3 The Reaction of p-C6H4FIF2 with CF3CO2H 48 3.7.2.4 The Reaction of p-C6H4FIF2 with aHF 49 3.8 Selected Reactivities of Iodonium Salts 52 3.8.1 Reactions with Lewis Bases 52 3.8.1.1 The Reaction of [p-C6H4F(CF2=CF)I][BF4] with Naked Fluoride 52 3.8.1.2 The Reaction of [p-C6H4F(C6H5)I][BF4] with Naked Fluoride 54 3.8.1.3 The 1 : 1 Reaction of [p-C6H4F(C6H5)I]F with Naked Fluoride in Dichloromethane 55 3.8.2 Reactions with Nucleophiles 56 3.8.2.1 The Reaction of [p-C6H4F(trans-CF3CF=CF)I][BF4] with (p-C6H4F)3As in CH2Cl2 56 3.8.2.2 The Reaction of [p-C6H4F(trans-CF3CF=CF)I][BF4] with (p-C6H4F)3P in CH2Cl2 56 3.8.2.3 The Reaction of [p-C6H4F(trans-CF3CF=CF)I][BF4] with 2,2´-Bipyridine in CH2Cl2 57 3.8.2.4 The Attempted Reaction of [p-C6H4F(CF2=CF)I][BF4] with (p-C6H4F)3P in aHF 58 Table of Contents IV 3.9 The Results of 1H, 13C, and 19F NMR Spectroscopic Studies 59 19 3.9.1 F NMR Spectroscopic Studies of IF5 59 3.9.2 The NMR Spectroscopic Studies of 4-Fluoro-1-(tetrafluoroiodo)benzene (p-C6H4FIF4) 59 3.9.3 The NMR Spectroscopic Studies of 4-Fluoro-1-(difluorooxoiodo)benzene (p-C6H4FIOF2) 60 3.9.4 The NMR Spectroscopic Comparison of C6H4XI, C6H4XI(OAc)2, and C6H4XIF2 (X = o-, m-, and p-F) 62 3.9.5 The Temperature Dependence of 19F NMR Chemical Shifts in Monofluoro(difluoroiodo)benzenes 67 3.9.6 NMR Spectroscopic Studies on Iodonium Salts 70 3.9.6.1 Asymmetric Diaryliodonium Tetrafluoroborates 70 3.9.6.2 trans-1,2,3,3,3-Pentafluoroprop-1-enyl(fluorophenyl)iodonium Tetrafluoroborates 72 3.9.6.3 Trifluorovinyl(fluorophenyl)iodonium Tetrafluoroborates 76 3.9.6.4 Alkenyl(pentafluorophenyl)iodonium Tetrafluoroborates 79 3.10 Thermal Stabilities of Selected (Difluoroiodo)benzenes and Aryl-Containing Iodonium Salts 81 3.11 X-Ray Crystal Structure Analysis 83 3.11.1 The Crystal Structures of p-C6H4FIF2 and o-C6H4FIF2 83 3.11.2 The Crystal Structure of [m-C6H4F(C6H5)I][BF4] 90 3.11.3 The Crystal Structure of [p-C6H4F(trans-CF3CF=CF)I][BF4] 94 3.11.4 The Crystal Structure of p-C6H4FIOF2 98 3.12 The Inductive and Resonance Parameters of Selected I(III)- Substituents in Iodonium Salts Using Taft`s Method 101 4 Experimental Section 104 4.1 Materials, Apparatus, and Methods 104 4.1.1 General Methods 104 4.1.2 Spectroscopic, Physical, and Analytical Measurements 105 Table of Contents V 4.1.2.1 NMR Spectroscopy 105 4.1.2.1.1 1H NMR Spectroscopy 105 4.1.2.1.2 11B NMR Spectroscopy 105 4.1.2.1.3 19F NMR Spectroscopy 105 4.1.2.1.4 13C NMR Spectroscopy 105 4.1.2.2 Differential Scanning Calorimetry (DSC) Measurements 107 4.1.2.3 Melting Point Measurements 107 4.1.2.4 X-Ray Single Crystal Measurements 107 4.1.2.5 Weighing of Electrostatic Materials 107 4.1.3 Solvents, Chemicals, and Starting Compounds 108 4.1.3.1 Solvents 108 4.1.3.2 Chemicals 109 4.1.3.2.1 Available in the Laboratory 109 4.1.3.2.2 Commercially Available Chemicals 109 4.1.3.3 Starting Compounds 111 4.1.3.3.1 The Preparation of (Diacetoxyiodo)arenes ArI(O2CCH3)2 111 4.1.3.3.2 The Preparation of Iodosylbenzenes ArIO 114 4.1.3.3.3 The Preparation of p-Fluoroiodylbenzene
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