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TAYLOR-DISSERTATION-2019.Pdf Copyright by William Victor Taylor 2019 The Dissertation Committee for William Victor Taylor Certifies that this is the approved version of the following Dissertation: Exploring the Interaction of Antimony Ligands with Late 3d Transition Metals: Enhancements in Metal Deposition, Magnetism and Luminescence through Heavy Atom Ligation Committee: Michael J. Rose, Supervisor Simon M. Humphrey Richard A. Jones Sean T. Roberts Xiaoqin Li Exploring the Interaction of Antimony Ligands with Late 3d Transition Metals: Enhancements in Metal Deposition, Magnetism and Luminescence through Heavy Atom Ligation by William Victor Taylor Dissertation Presented to the Faculty of the Graduate School of The University of Texas at Austin in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy The University of Texas at Austin May 2019 Dedication To my family: Thank you for all your love and support over the years. You kept me grounded and reminded me what was important through all of this. I love you all. Acknowledgements Mike: You taught me so much about chemistry and were a truly excellent role model. Thank you for all of your guidance and support. My friends: Thanks for all the fun times and distractions necessary to get through grad school. I’m going to miss our hang outs and game sessions. The Rose group: Thanks for all the fantastic conversations—especially the ones that burned through sub-group time. I couldn’t have asked for a better group of co-workers and friends, good luck in all of your endeavors. v Abstract Exploring the Interaction of Antimony Ligands with Late 3d Transition Metals: Enhancements in Metal Deposition, Magnetism and Luminescence through Heavy Atom Ligation William Victor Taylor, Ph. D. The University of Texas at Austin, 2019 Supervisor: Michael J. Rose Antimony has been known to civilizations for thousands of years, and its role in cosmetics, metallurgy and alchemy helped shape the course of history. However, as a useful ligand in metal complex syntheses, organoantimony compounds have been largely ignored. This work explores the ligand syntheses and capabilities of both monodentate and polydentate antimony compounds towards higher valent (MII/I) late row 3d transition metals, namely nickel(II), copper(I), and cobalt(II). A large library of homo- and i t heteroleptic antimony ligands with general structure SbR3 (R = Me, Ph, Pr, Cy, Bu) were synthesized and characterized, and their successful complexation to metal halides afforded several novel complexes and crystal structures. Slight modifications to the steric and electronic properties of the antimony ligands were shown to drastically affect the coordination number, geometry, and pertinent reactivities and properties of the final metal- antimony complexes. More specifically, synthesized nickel-antimony complexes performed electroless deposition of a Cu/Ni alloy onto the surface of a Cu|Si substrate. It was determined that the electronic properties of the ligands had a direct effect on surface purity, as the strongest σ-donating ligands were able to more readily scavenge impurities vi from the deposition solution. Among copper-antimony complexes, the steric size of the ligand dictated the formation of dimers (small ligands), or cuboids (large ligands), which displayed NIR thermoluminescent properties. A thorough investigation of the structure- luminescence correlation in these complexes revealed that short Cu-Cu bonds (ligand %Vbur ~ 27.0 %) inside the cuboid core and high complex symmetry (cubic) held co- responsibility for red-shifting emission wavelengths. Paramagnetic cobalt-antimony complexes were synthesized, and these complexes showed a significant increase in the extent of axial zero-field-splitting (D) versus analogous phosphine compounds, which has been attributed to an increase of spin-orbit-coupling on the metal center originating from the ligands. The translational spin-orbit-coupling donated to a 3d metal center from heavy donor ligands could help improve C-H activation catalytic activity in these new complexes via a higher probability of spin-crossover transitions and a stabilization of transition state energies. Although the cobalt-antimony complexes displayed signs of increased reactivity towards traditional C-H activation substrates, the results were preliminary and overall inconclusive. vii Table of Contents List of Tables .....................................................................................................................xv List of Figures ................................................................................................................. xvii List of Schemes ................................................................................................................xxv Chapter 1: The Role of Antimony in the Pursuit of Novel C-H Activation Catalysts: An Elemental and Synthetic History of Antimony Ligands, Metal Complexes, and Alchemy .........................................................................................................................1 1.1 The History of Antimony: From Makeup to Weaponry .......................................1 1.2 General Properties of Antimony ...........................................................................6 1.3 Antimony Ligand Syntheses .................................................................................7 1.3.1 Monodentate Antimony Ligands ...........................................................7 1.3.2 Multidentate Antimony Ligands ..........................................................11 1.4 Antimony-Metal Complexes...............................................................................13 1.4.1 Monodentate Sb-Metal complexes ......................................................14 1.4.2 Multidentate Sb-Metal complexes .......................................................15 1.5 Metal Complexes with Alkyl-Based Sb Ligands ................................................16 1.6 C-H Activation Catalysts and Spin-Orbit-Coupling ...........................................17 1.7 Translational Spin-Orbit-Coupling through Heavy Atom Ligation ...................22 1.8 Antimony Ligands towards Translational SOC and Other Avenues Worth Exploring for Sb-Metal Complexes ....................................................................26 1.9 References ...........................................................................................................28 Chapter 2: Syntheses, Structures and Characterization of Nickel(II) Stibines: Steric and Electronic Rationale for Metal Deposition ...........................................................38 2.0 Prologue ..............................................................................................................38 2.1 Introduction .........................................................................................................39 viii 2.2 Experimental .......................................................................................................42 2.2.1 Reagents and General Procedures........................................................42 2.2.2 Ligand Syntheses .................................................................................42 2.2.2.1 Safety Precaution. ....................................................................42 i 2.2.2.2 Triisopropylantimony (Sb Pr3) .................................................44 i 2.2.2.3 Diisopropylphenylantimony (Sb Pr2Ph) ...................................45 2.2.2.4 Dimethylphenylantimony (SbMe2Ph) ......................................46 2.2.2.5 Diphenylmethylantimony (SbPh2Me) ......................................46 2.2.3 Synthesis of the Metal Complexes.......................................................47 i 2.2.3.1 Ni(I)2(Sb Pr3)2 (1) .....................................................................47 i 2.2.3.2 Ni(I)2(Sb Pr2Ph)2 (2) ................................................................47 2.2.3.3 Ni(I)2(SbMe2Ph)3 (3) ...............................................................48 2.2.3.4 Ni(I)2(SbMePh2)3 (4) ...............................................................48 i 2.2.3.5 Ni(I)2(Sb Pr3)2CO (5) ...............................................................49 i 2.2.3.6 Ni(I)2(Sb Pr2Ph)2CO (6) ...........................................................49 2.2.3.7 Ni(I)2(SbPh3)2 ..........................................................................50 i 2.2.3.8 [Ni(I)3(Sb Pr3)][NBu4] .............................................................50 2.2.4 General Metal-Deposition Procedure ..................................................50 2.2.5 Physical Measurements........................................................................51 2.2.6 X-ray Data Collection ..........................................................................51 2.2.7 DFT Calculations .................................................................................52 2.3 Results and Discussion .......................................................................................53 2.3.1 Synthesis and Rationale .......................................................................53 ix 2.3.2 X-ray Structures and Steric Ligand Substituent Effects ......................55 i i 2.3.2.1 Ni(I)2(Sb Pr3)2 (1) and Ni(I)2(Sb Pr2Ph)2 (2) ............................55 2.3.2.2 Ni(I)2(SbMe2Ph)3 (3) and Ni(I)2(SbMePh2)3 (4)......................57 i 2.3.2.3 Ni(I)2(Sb Pr3)2CO (5) ...............................................................60 i 2.3.2.4 Ni(I)2(Sb Pr2Ph)2CO (6) ...........................................................62
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