Brigham Young University BYU ScholarsArchive All Theses and Dissertations 2019-03-01 Selective Catalysis by Polymer-Supported Ruthenium NanoparticlesAND New Ligand Design for Cooperative and Bimetallic Catalysis Seyed Hadi Nazari Brigham Young University Follow this and additional works at: https://scholarsarchive.byu.edu/etd BYU ScholarsArchive Citation Nazari, Seyed Hadi, "Selective Catalysis by Polymer-Supported Ruthenium NanoparticlesAND New Ligand Design for Cooperative and Bimetallic Catalysis" (2019). All Theses and Dissertations. 7386. https://scholarsarchive.byu.edu/etd/7386 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in All Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Selective Catalysis by Polymer-Supported Ruthenium Nanoparticles AND New Ligand Design for Cooperative and Bimetallic Catalysis Seyed Hadi Nazari A dissertation submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Doctor of Philosophy David J. Michaelis, Chair Steven L. Castle Joshua L. Price Daniel H. Ess Roger G. Harrison Department of Chemistry and Biochemistry Brigham Young University Copyright © 2019 Seyed Hadi Nazari All Rights Reserved ABSTRACT Selective Catalysis by Polymer-Supported Ruthenium Nanoparticles AND New Ligand Design for Cooperative and Bimetallic Catalysis Seyed Hadi Nazari Department of Chemistry and Biochemistry, BYU Doctor of Philosophy The abstract is the summary of three different projects all centered around the general idea of catalysis which is the general theme of research in the Michaelis laboratory. The first project focuses on development of a new heterogeneous catalyst for selective catalysis. In the Michaelis lab, we were interested in the potential of nanoparticle catalysts for regioselective transformations. We showed that polymer supported ruthenium nanoparticles performed as a reliable catalyst for regioselective reduction of azide to amine. In our study of regioselective reduction of multiple azide containing substrates, we observed that in presence of our ruthenium nanoparticle catalysts, the least sterically hindered azide group reduced to amine functional group. The results were complementary to the conventional methods that employ triphenyl phosphine (Staudinger reaction) as the reductant and target the most electronically active azide group. In the second project, we were looking to develop a new class of hetero-bimetallic Nickel-Titanium complexes as an efficient catalyst for organic transformations. We designed and synthesized numerous bidentate ligands including NHC-Phosphine ligand. Our kinetic studies on the Suzuki cross coupling of allylic alcohols and phenyl boronic esters showed that the bidentate nature of the ligand was necessary for the success of the catalytic process. The ligand was proved to stabilize the catalyst in the solution by increasing the lifetime of the nickel (0) in the reaction medium. We also discovered a new cooperative titanium-nickel system for mild allylic amination of allyl alcohols. The system also represents an ideal catalyst for tandem cyclization amination process. In the Michaelis lab, we were also interested to explore the ability of bimetallic complexes in C-H functionalization process. Our efforts in this project led to the discovery of new Pallladium dimer complexes with two palladium centers in oxidation state of (I). The catalyst showed unique reactivity in C-C bond activation/functionalization. We have also discovered that in presence of catalytic amount of triflic acid and stoichiometric amount of phenyl boronic acid, cinnamyl alcohol undergoes a boron template dimerization/cyclization. The reaction represents a great synthetic pathway for the synthsis of bis homoallylic alcohols. Keywords: nanoparticle catalysis, nickel catalyst, regioselective reduction, C-H activation ACKNOWLEDGEMENTS I would like to express my sincere appreciation and gratitude to all those who helped me to finish this work and write this dissertation at Brigham Young University. I am indebted to my family for their support without which I could not have moved through this tortuous path. I would like to thank my parents for their prayers and warm support. Particular thanks to Prof. David J. Michaelis for his guidance during my research. Prof. Michaelis helped me to think independently, and be a better writer and researcher. The energy, enthusiasm, and encouragement I received from him have been key factors in my success. I would also like to thank all the committee members, Dr. Josh L. Price, Steven L. Castle, Roger G. Harrison, Daniel H. Ess, and David J. Michaelis for their support and inspiring suggestions and comments through my dissertation, proposal, and annual evaluations. I am very grateful to all the students, technicians, and Professors including, Shenglou Deng, Venkata Reddy Udumula, Ankur Jalan, Marjan Hashemi, Concordia Lo, Michael Kinghorn, Chloe Ence, Karissa Kenney, Gabriel Valdivia, Yu Cai, Erin Martinez, Jordan Tretbar, Jacob Parkman, Kari Van Sickel, Dr. Matt. A. Linford and Dr. Scott R. Burt who provided assistance during my research. This work was mainly supported by the PRF, NSF, and Brigham Young University. TABLE OF CONTENTS TITLE PAGE .............................................................................................................................. i ABSTRACT ............................................................................................................................... ii ACKNOWLEDGEMENTS ..................................................................................................... iii TABLE OF CONTENTS .......................................................................................................... iv LIST OF FIGURES ............................................................................................................... viii LIST OF TABLES ................................................................................................................. xiii Chapter 1 Catalysis by Polystyrene-Supported Ruthenium Nanoparticle Catalysts ........ 1 1.1 Introduction .......................................................................................................... 1 1.2 Synthesis of Nanoparticle Catalysts: A General Overview ................................. 2 1.3 The Impact of Nanoparticle Shape on Catalytic Activity .................................... 3 1.4 The Impact of Nanoparticle Size on Catalytic Activity ....................................... 5 1.5 Application of Polymer Incarcerated Nanoparticles in Organic Reactions ......... 6 1.5.1 Asymmetric transformations with chiral modified ligand nanoparticle catalysts: ........................................................................................... 8 1.5.2 Chemo- and regioselective transformations by nanoparticle catalysts: ............................................................................................................... 10 1.6 Site-Selective Alkyl and Azide Reductions with Heterogeneous Nanoparticle Catalysts ................................................................................................. 11 1.7 Results and Discussion ...................................................................................... 12 1.8 Synthesis of Aryl-Hydroxylamines via Partial Reduction of Nitroaryls with Soluble Nanoparticles .......................................................................................... 18 1.8.1 Results and discussion ............................................................................ 18 1.9 Experimental Procedures and Supporting Data for Chemo and Site Selective Azide Reduction with Heterogeneous Nanoparticle Catalysts. ............ 21 iv 1.9.1 General information ................................................................................ 21 1.9.2 Synthesis and characterization of Ru NP`s@polystyrene ...................... 21 1.9.3 Preparation of the sample for ICP-analysis ............................................ 22 1.9.4 Characterization of Ru/polystyrene nanopartices ................................... 22 1.9.5 Experimental procedures ........................................................................ 23 1.9.5.1 General procedure: reduction of (E)-1-azidohex-3-ene ........................ 23 1.9.5.2 Reuse experiments of Ru NP`s@polystyrene ....................................... 24 1.9.5.3 Experimental procedures and spectral data .......................................... 24 1.10 Experimental Procedures and Supporting Data for the Synthesis of Arylhydroxylamines via Partial Reduction of Nitroarenes with Nanoparticle Catalysts ................................................................................................. 56 1.10.1 General information ................................................................................ 56 1.10.2 Synthesis and characterization of Ru NP’s in polystyrene ..................... 57 1.10.3 Preparation of the sample for ICP-analysis ............................................ 58 1.10.4 Characterization of Ru/polystyrene nanoparticles .................................. 58 1.10.5 Experimental procedures ........................................................................ 58 1.10.5.1 General procedure for the synthesis of N- aryl hydroxylamines: ......... 58 1.10.5.2 Large scale reaction