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Synthesis and Coordination Chemistry of Water-Soluble Phosphines: Application to Ru-Catalyzed Hydration of Nitriles in Aqueous and Biphasic Media

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Synthesis and Coordination Chemistry of Water-Soluble Phosphines: Application to Ru-Catalyzed Hydration of Nitriles in Aqueous and Biphasic Media University of Nevada, Reno Synthesis and Coordination Chemistry of Water-Soluble Phosphines: Application to Ru-Catalyzed Hydration of Nitriles in Aqueous and Biphasic Media A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by Wei-Chih Lee Dr. Brian J. Frost/Dissertation Advisor December, 2011 THE GRADUATE SCHOOL We recommend that the dissertation prepared under our supervision by WEI-CHIH LEE entitled Synthesis And Coordination Chemistry Of Water-Soluble Phosphines: Application To Ru-Catalyzed Hydration Of Nitriles In Aqueous And Biphasic Media be accepted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Brian J. Frost, Ph. D., Advisor Vincent J. Catalano, Ph. D., Committee Member Christopher S. Jeffrey, Ph. D., Committee Member Manoranjan Misra, Ph. D., Committee Member Keith E. Dennett, Ph. D., Graduate School Representative Marsha H. Read, Ph. D., Associate Dean, Graduate School December, 2011 i Abstract This dissertation investigates the synthesis and characterization of a series of 1,3,5-triaza-7-phosphaadamantane (PTA) derivatives and their ruthenium arene complexes as potential water-soluble catalysts for aqueous and biphasic hydration of nitrile. A series of upper-rim modified PTA derivatives were prepared by reaction of lithiated PTA with various electrophilic substrates, including aldehydes, ketones, imines 1 2 and CO2. Monodentate κ -P and bidentate κ -P,O and P,N coordination modes were observed in Ru arene complexes of the newly synthesized phosphine ligands. Ruthenium arene complexes of β-aminophosphines PTA-CR1R2NHPh were synthesized and exhibited hemilabile behavior. All compounds were structurally characterized both in solution (multinuclear (1H, 13C, 31P) NMR spectroscopic studies, and ESI-MS) and in the solid state (IR, and single-crystal X-ray crystallography). The air-stable and water-soluble ruthenium arene complexes are active in catalytic hydration of nitriles to amides in water at 100 °C under air with tolerance toward ether, hydroxyl, nitro, bromo, aldehyde, pyridyl, benzyl, and alkyl functional groups. [RuCl2(PTA)4] is a highly active catalyst for aqueous nitrile hydration. Near quantitative conversion of aromatic, alkyl, and vinyl nitriles to their corresponding amides was observed. The reaction tolerated ether, hydroxyl, nitro, bromo, formyl, pyridyl, benzyl, alkyl, and olefinic functional groups. Some amides were isolated by simple decantation from the aqueous phase catalyst. Catalyst loading down to 0.001 mol% was examined with turnover numbers as high as 22000 observed. The catalyst was stable for weeks in solution and could be reused more than five times without significant loss of activity. ii Six group 12 metal complexes of PTA and derivatives, [ZnCl2(PTA)2], [ZnCl2(O=PTA)(H2O)], [ZnCl2(μ-O=PTA)]n, [HgCl2(μ-O=PTA)]n, [ZnCl2(S=PTAH)(S=PTAZnCl3)], and [CdCl2(S=PTA)(CH3OH)]n, have been synthesized, and characterized by IR, elemental analysis, ESI-MS, 1H and 31P{1H} NMR, and single-crystal X-ray analysis. Their structures and coordination modes are investigated both in the solid state and in aqueous solution. Their solid-state structures, found to be either dinuclear or polymeric, were elucidated by single-crystal X-ray diffraction. All the metal complexes, however, do not remain intact in aqueous solution as revealed by their 1H and 31P{1H} NMR spectroscopic data, and electrospray ionization mass spectrometry. iii Acknowledgements First and foremost, I would like to thank my advisor Professor Brian J. Frost for his guidance and encouragement throughout my graduate study. I feel fortunate to have had the opportunity to work in the Frost research group. He is also a great teacher; I learned a lot from his classes in Advanced Inorganic Chemistry and Organometallic Chemistry. I would like express my gratitude to my committee members: Prof. Brian J. Frost, Prof. Vincent J. Catalano, Prof. Christopher S. Jeffrey, Prof. Manoranjan Misra, Prof. Keith E. Dennett for reading my dissertation and giving me valuable advice. I would like to thank our faculty members for inviting a lot of organic and inorganic chemists from outside the university to give seminars in the department. I really enjoy these seminars and learn a lot from them. I am grateful to Prof. John H. Nelson the best NMR class I have ever had. I would like thank previous and current Frost group members Dr. Rongcai Huang, Dr. Tae Ho Kim, Prof. Charles Mebi, Prof. Radhika Nair, Gene Wong, Jennifer Harkreader, Jason Weeden, Raphel Enow, Jocelyn Pineda, Kathryn Galloway and Jeremiah Sears for their friendship. I appreciate our support staff in the Chemistry department for their great help. Special thanks to Jennifer Melius, Roxie Taft, and Jenny Costa. I would like to thank Dr. Stephen M. Spain for his great help with the NMR and GC-MS instruments. I also appreciate our great facilities and instruments in the department, especially nuclear magnetic resonance spectrometers, ESI-MS spectrometer, GC-MS spectrometer, the iv Bruker-Nonius SMART Apex CCD-based single crystal diffractometer, and high performance Beowulf computer clusters. And finally, last but certainly not least, I want to thank the most important and adorable person in my life, my significant other, Prof. Hui-Chun Yang, for all of her support and love. I would like to thank my parents, Chin-Yan Lee and Yueh-Chin Lin, and my sister, Chen-I Lee, who throughout my life have always given me all of the support and encouragement that I needed. Without them, I could not finish this study. v Table of Contents Abstract i Acknowledgements iii Table of Contents v Compound Numbers ix List of Figures xi List of Schemes xviii List of Tables xx Chapter 1. Introduction and Background 1 1.1 Aqueous Biphasic Catalysis 1 1.2 Water-soluble Phosphines 3 1.3 Chemistry of 1,3,5-triaza-7-phosphaadamantane (PTA) 4 1.3.1 Synthesis and Properties of PTA 4 1.3.2 Applications 7 1.4 Organization and Scope 8 1.5 References 10 Chapter 2. Insertion of Aldehydes, Ketones, Carbon Dioxide, and Imines into the C-Li Bond of 1,3,5-Triaza-7-phosphaadamantan-6-yllithium 12 2.1 Introduction 12 2.1.1 PTA Derivatives in the Literature 12 2.1.2 PTA Upper-rim Modification 14 2.2 Results and Discussion 17 vi 2.2.1 Addition of CO2 17 2.2.2 Addition of Ketones 18 2.2.3 Addition of Pyridinecarboxaldehydes 22 2.2.4 Addition of Imines 28 2.2.5 Addition of Nitriles 36 2.2.6 Attempted Iodination 39 2.2.7 Attempted Synthesis of Bis-PTA Adduct 41 2.3 Concluding Remarks 43 2.4 Experimental 44 2.4.1 Materials & Methods 44 2.4.2 X-ray Crystallography 45 2.4.3 Computational Details 45 2.4.4 Water Solubility 45 2.4.5 Synthesis 46 2.5 References 64 Chapter 3. Ruthenium Arene Complexes of PTA Derivatives 66 3.1 Ruthenium Arene Complexes 66 3.2 Results and Discussion 68 3.2.1 Ruthenium Arene Complexes of PTA-CR2OH 68 3.2.2 Ruthenium Arene Complex of PTA-CO2Li 71 3.2.3 Ruthenium Arene Complexes of PTA-CHpyOH 73 3.2.4 Ruthenium Arene Complexes of PTA-CR1R2NHPh 84 vii 3.3 Concluding Remarks 91 3.4 Experimental 92 3.4.1 Materials & Methods 92 3.4.2 X-ray Crystallography 93 3.4.3 Synthesis 93 3.5 References 104 Chapter 4. Aqueous and Biphasic Ruthenium-catalyzed Nitrile Hydration under Atmospheric Conditions 106 4.1 Introduction 106 4.2 Results and Discussion 110 4.2.1 Catalyst Evaluation and Screening 110 4.2.2 Nitrile Hydration by Ruthenium Arene Complexes 113 4.2.3 Nitrile Hydration by [RuCl2(PTA)4] 117 4.2.4 Aqueous and Biphasic Recycling Experiments for Nitrile Hydration 127 4.3 Concluding Remarks 129 4.4 Experimental 130 4.4.1 Materials & Methods 130 4.4.2 General Procedure for the Catalytic Nitrile Hydration Reactions 132 4.5 References 134 Chapter 5. Synthesis, Structure, and Coordination Chemistry of PTA, PTA Oxide, and PTA Sulfide with Borane, Manganese, Group 12 Metals, and Silver 136 5.1 Introduction 136 viii 5.1.1 Coordination Chemistry of PTA 137 5.1.2 Coordination Chemistry of PTA Oxide and PTA Sulfide 139 5.2 Results and Discussion 139 5.2.1 BH3 Complex of PTA 139 5.2.2 Mn(II) Complex of PTA 141 5.2.3 Group 12 Metal Complexes of PTA, O=PTA, and S=PTA 145 5.2.4 Ag(I) Complex of PTA Oxide 157 5.3 Concluding Remarks 158 5.4 Experimental 159 5.4.1 Materials & Methods 159 5.4.2 X-ray Crystallography 160 5.4.3 Synthesis 160 5.5 References 167 Chapter 6. X-ray Crystallography 169 6.1 Introduction 169 6.2 Experimental 169 6.3 Results 171 Chapter 7. General Conclusions 183 APPENDIX 185 CURRICULUM VITAE 200 ix Compound Numbers Compound Number Compound Number 1 9 2 10 3 11 4 12 5 13 6 14 7 15 8 [16]Cl x 17 25 [18]Cl [CdCl2(PTA)]n 26 [19]Cl [ZnCl2(O=PTA)(OH2)] 27 [20]Cl [ZnCl2(O=PTA)]n 28 21 [HgCl2(O=PTA)]n 29 4 [(H3B)4(μ -PTA)] 22 [ZnCl2(S=PTAH)(S=PTA-ZnCl3)] 30 23 [CdCl2(S=PTA)(CH3OH)]n 31 24 [Ag(OH2)(NO3)(O=PTA)]n 32 xi List of Figures Figure Page 1.1 A schematic illustration of aqueous biphasic catalysis. 2 1.2 Some examples of water-soluble phosphines. 4 31 1 1.3 P{ H} NMR spectra of PTA in CDCl3 (top) and D2O (bottom). 6 1 1.4 H NMR spectra of PTA in CDCl3 (top) and D2O (bottom).
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