Investigations Into Alkene Hydration and Alkene Oxidation Catalysis
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Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2013 Investigations into alkene hydration and alkene oxidation catalysis William Schreiter Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Schreiter, William, "Investigations into alkene hydration and alkene oxidation catalysis" (2013). LSU Doctoral Dissertations. 473. https://digitalcommons.lsu.edu/gradschool_dissertations/473 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. INVESTIGATIONS INTO ALKENE HYDRATION AND ALKENE OXIDATION CATALYSIS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy In The Department of Chemistry by William James Schreiter B. A., Lawrence University, 2004 May 2013 TABLE OF CONTENTS ABSTRACT .......................................................................................................................................v CHAPTER 1. INTRODUCTION .....................................................................................................1 1.1 Alkene Hydration ...................................................................................................................1 1.2 Alkene Oxidation ...................................................................................................................9 1.3 References ..............................................................................................................................20 CHAPTER 2. INVESTIGATION INTO ALKENE HYDRATION CATALYSIS .........................27 2.1 Motivation ..............................................................................................................................27 2.2 Attempted Alkene Hydration Catalysis with Ni/Phosphine Complexes ...............................29 2.3 Attempted Hydration Catalysis Utilizing Other Metal/Phosphine Complexes .....................33 2.4 The White Solid “Product” – How to Waste a Year in Graduate School and Get Your Advisor Excited (at least initially) ...............................................................................................36 2.5 Catalytic Screening for Possible Alkene Hydration Catalysis ...............................................40 2.6 Conclusions ............................................................................................................................45 2.7 References ..............................................................................................................................47 CHAPTER 3. INVESTIGATION INTO ALKENE OXIDATION CATALYSIS UTILIZING Ni/PHOSPHINE COMPLEXES ................................................................................49 3.1 Motivation ..............................................................................................................................49 3.2 Alkene Oxidative Cleavage via Bimetallic Ni/Phosphine Complexes ..................................51 3.3 Identification of the Broad Resonances .................................................................................65 3.4 Monometallic Metal Complexes as Possible Oxidative Cleavage Catalysts .........................72 3.5 Other Oxidizing Agents .........................................................................................................74 3.6 Mechanistic Possibilities ........................................................................................................76 3.7 Conclusions ............................................................................................................................83 1 31 1 CHAPTER 4. H AND P{ H} NMR STUDIES OF RAC- AND MESO-Ni2Cl4(et,ph-P4), Ni21R and Ni21M ......................................................................................................87 4.1 Introduction ............................................................................................................................87 4.2 Ni2Cl4(meso-et,ph-P4), Ni21M, and Ni2Cl4(rac-et,ph-P4), Ni21R ........................................89 4.3 Effect of Water on Ni21M......................................................................................................92 4.4 Effect of the Organic Solvent on the Reaction Between Ni21M and Water ..........................96 4.5 Varying the Concentration of Water ......................................................................................104 4.6 Identification of F and Attempts to Synthesize A, B and C ..................................................107 4.7 Ni21R and Water ....................................................................................................................112 4.8 Effect of Other Additives on the Reaction (NaCl, O2. Inhibitors, Heat) ...............................119 4.9 Conclusions and Proposals ....................................................................................................124 4.10 References ............................................................................................................................134 CHAPTER 5. SYNTHESIS, SEPARATION AND CHARACTERIZATION OF 2R AND 2M AND Ni22M AND Ni22R ..........................................................................................135 5.1 Introduction ............................................................................................................................135 5.2 Synthesis and Characterization of 2R and 2M ......................................................................136 5.3 Synthesis and Separation of Ni22M and Ni22R .....................................................................138 ii 5.4 Cyanolysis of Ni22M and Ni22R and Isolation of the Pure Diastereomers ...........................141 5.5 Preliminary Investigation into the Solution-State Chemistry and Reactivity of Ni22M and Ni22R ...........................................................................................................................................146 5.6 Conclusions ............................................................................................................................148 5.7 References ..............................................................................................................................150 CHAPTER 6. EXPERIMENTAL PROCEDURES ..........................................................................152 6.1 General ...................................................................................................................................152 6.2 Attempts at Alkene Hydration Catalysis................................................................................153 6.2.1 General Comments........................................................................................................153 6.2.2 Reaction Types..............................................................................................................154 6.2.3 Reaction Table ..............................................................................................................155 6.3 Hydration Screening Experiments .........................................................................................169 6.3.1 The Ligand Solution .....................................................................................................169 6.3.2 Reaction Setup ..............................................................................................................169 6.3.3 Reaction Table ..............................................................................................................170 6.4 Oxidative Cleavage Reactions ...............................................................................................173 6.4.1 Reaction Types..............................................................................................................173 6.4.2 Reaction Tables .............................................................................................................173 6.5 NMR Reactions ......................................................................................................................183 6.5.1 Reaction Conditions When Acetone-d6 was Utilized ...................................................183 6.5.2 Reaction Conditions When CD3CN or DMSO-d6 was Utilized ...................................183 6.5.3 Reaction Table ..............................................................................................................184 6.6 Ni21M Under Balloon Pressure O2 ........................................................................................187 6.6.1 Acetone and Water ........................................................................................................187 6.6.2 Acetonitrile and Water ..................................................................................................187 6.6.3 DMSO and Water .........................................................................................................187 6.6.4 Added Substrate ............................................................................................................187