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Reactivity Studies of Catalytically Relevant Palladium Model Complexes

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Reactivity Studies of Catalytically Relevant Palladium Model Complexes Reactivity Studies of Catalytically Relevant Palladium Model Complexes by Ansis Maleckis A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) in The University of Michigan 2014 Doctoral Committee: Professor Melanie S. Sanford, Chair Professor Mark Banaszak Holl Professor Erdogan Gulari Professor John P. Wolfe © Ansis Maleckis 2014 Acknowledgements I would like to thank my advisor, Professor Melanie Sanford for having me as a member of her research group. I thank you for your ideas, suggestions and unceasing enthusiasm for research and science. You taught me how to explore, write and present chemistry. I am extremely grateful to you also for your infinite understanding and tolerance towards my unruly and idiosyncratic personality. I thank my dissertation committee members, Professors John P. Wolfe, Mark Banaszak Holl and Erdogan Gulari for their invaluable time and advice. I must thank the department staff for all the help they have provided. DRs. Eugenio Alvarado and Chris Kojiro for assistance with NMR experiments, DRs Jim Windak and Paul Lennon for Mass spectrometry analyses and Dr Jeff W. Kampf for X-ray structures. ii Table of Contents Acknowledgments......................................................................................................ii List of Tables .............................................................................................................vi List of Schemes ..........................................................................................................vii List of Figures ............................................................................................................xii Abstract ......................................................................................................................xv Chapter 1 Introduction ................................................................................................................1 1.1 Reactivity Studies of Well Defined Palladium(IV) Centers ............................1 1.2 Studies towards Nickel and Palladium Catalyzed Trifluoromethylation .........6 1.3 References ........................................................................................................9 Chapter 2 Design and Synthesis of Palladium(IV) Model Complexes Supported by Facial Tridentate Ligands .....................................................................................................11 iii 2.1 Introduction ..........................................................................................................11 2.2 Synthesis of Supporting fac-L2X Ligands ...........................................................11 II 2.3 Preparation of (fac-L2X)Pd (Aryl)(CF3) Complexes ..........................................13 IV 2.4 Preparation and Reactivity of (fac-L2X)Pd (Aryl)(CF3)(Hal) Complexes .........17 2.5 Conclusions ..........................................................................................................29 2.6 Experimental Section ...........................................................................................29 2.7 References ............................................................................................................59 Chapter 3 Investigation of C–H Activation at Palladium(IV) ....................................................61 3.1 Introduction ..........................................................................................................61 IV 3.2 Synthesis of the [(Py3CH)Pd (biphenyl)Cl2]X Model System ...........................64 3.3 Reactivity of the Model Complexes ....................................................................68 3.4 Proposed Mechanism of C–H Activation at Palladium(IV) ................................71 3.5 Ligand Substitution at Palladium(IV) ..................................................................73 IV 3.6 Rotation about the Pd –CAryl Bond .....................................................................78 3.7 Configurational Isomerization at PdIV via Berry Pseudorotation ........................80 3.8 Acetate Assisted C–H Cleavage at Palladium(IV) ..............................................82 3.9 Regioselectivity of C–H Activation at Palladium(IV) .........................................85 3.10 Conclusions ........................................................................................................87 3.11 Experimental Section .........................................................................................88 3.12 References ..........................................................................................................140 iv Chapter 4 Synthesis of Trifluoromethyl Complexes Using TFAA as CF3 Source ....................142 4.1 Introduction ..........................................................................................................142 4.2 Decarbonylative Synthesis of Nickel Trifluoromethyl Complexes .....................146 4.3 Decarbonylative Synthesis of PdII Trifluoromethyl Complexes ..........................150 4.4 Reactivity of the Perfluoroalkyl Nickel and Palladium Complexes ....................156 4.5 Conclusions ..........................................................................................................157 4.6 Experimental Section ...........................................................................................158 4.7 References ............................................................................................................179 Chapter 5 Catalytic Cycle of Trifluoromethylation with TFAA as a CF3 Source ......................181 5.1 Introduction ..........................................................................................................181 0 5.2 Oxidative Addition of TFA Esters to (RuPhos)nPd ............................................184 5.3 Decarbonylative Decomposition of (RuPhos)Pd(CORf)(OCORf).......................186 5.4 Transmetallation and Reductive Elimination.......................................................189 5.5 Conclusions ..........................................................................................................191 5.6 Experimental Section ...........................................................................................191 5.7 References ............................................................................................................205 v List of Tables Chapter 2 Design and Synthesis of Palladium(IV) Model Complexes Supported by Facial Tridentate Ligands IV Table 2.1 Preparation of (fac-L2X)Pd (Aryl)(CF3)(Cl) complexes ................................. 19 II Table 2.2 Reactions of (dpaa)Pd (Aryl)(CF3) with NFTPT ............................................. 20 Chapter 3 Investigation of C–H Activation at Palladium(IV) Table 3.1 Spin-lattice relaxation times (T1) for complexes 7, 8 and 9.............................. 66 IV + Table 3.2 MS data of [(Py3CH)Pd ([1,1'-biphenyl]-2,2’-diyl)(Cl)] (12) ..................... 137 Table 3.3 MS data for intramolecular KIE determination .............................................. 137 vi List of Schemes Chapter 1 Introduction Scheme 1.1 Diastereoselective Csp3-H iodination.............................................................. 2 Scheme 1.2 Acetoxylation and arylation of unactivated Csp3-H bonds ............................. 2 Scheme 1.3 Synthesis of TP and BiPy supported PdIV complexes ..................................... 3 Scheme 1.4 Formation of PdIV via oxidative addition of aryliodide to PdII ....................... 4 Scheme 1.5 Oxidative PdIV mediated fluorination of arylboronic acids ............................ 4 Scheme 1.6 Directed PdIV mediated C–H chlorination ...................................................... 5 Scheme 1.7 Directed PdIV mediated C–H sulfonylation ..................................................... 5 Scheme 1.8 Catalytic cycle for proposed trifluoromethylation reaction ............................ 8 Chapter 2 Design and Synthesis of Palladium(IV) Model Complexes Supported by Facial Tridentate Ligands Scheme 2.1 Synthesis of fac-L2X ligands 2 and 3 ............................................................ 13 Scheme 2.2 Synthesis of fac-L2X ligand 4 ....................................................................... 13 Scheme 2.3 Preparation of cis-(4-Mepy)2Pd(4-MeC6H4)(CF3) ........................................ 14 vii II Scheme 2.4 Preparation of (Tp)Pd (4-MeC6H4)(CF3)...................................................... 15 II Scheme 2.5 Preparation of (L2X)Pd (4-MeC6H4)(CF3) complexes ................................. 15 IV Scheme 2.6 Preparation of (Tp)Pd (Aryl)(CF3)(Cl) ........................................................ 18 IV Scheme 2.7 Reactivity of (Tp)Pd (Aryl)(CF3)(Cl) .......................................................... 18 IV Scheme 2.8 Reaction of (dpsa)Pd (Aryl)(CF3)(F) with TMSOTf .................................. 23 IV Scheme 2.9 Synthesis of (dpph)Pd (Aryl)(CF3)(Cl) ....................................................... 24 IV Scheme 2.10 Reactivity of of (dpph)Pd (Aryl)(CF3)(Cl) with L-type ligands ............... 26 IV Scheme 2.11 Reactivity of of (dpph)Pd (Aryl)(CF3)(Cl) with X-type ligands ............... 27 Scheme 2.12 Preparation of (dpph)PdIV(biphe)(Cl) ......................................................... 28 Chapter 3 Investigation of C–H Activation at Palladium(IV) Scheme 3.1 para-Selective arylation of monosubstituted arenes ...................................... 61
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