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CO2 Activation and Redox Activity of NN

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CO2 Activation and Redox Activity of NN To ancillary and beyond: CO 2 activation and redox activity of NN chelate actor ligands by Trevor William Janes A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Toronto © Copyright by Trevor Janes 2017 To ancillary and beyond: CO 2 activation and redox activity of NN chelate actor ligands Trevor William Janes Doctor of Philosophy Department of Chemistry University of Toronto 2017 Abstract This thesis examines the fundamental coordination chemistry and subsequent reactivity of actor and redox-active ligands. In this context, the two NN chelate ligand classes that are explored are 4,5-diazafluorene and o-phenylenediamine. In Chapter 2, actor diazafluorenyl ligands were explored. New Ru and Zn diazafluorenyl complexes undergo C–H borylation of the diazafluorenyl ligand to form the corresponding diazafluorenylboronic ester complexes, which can insert CO 2 into their C–B bonds to form boryl ester functionalities. The relevance of this new reactivity to catalytic CO 2 reduction was also explored. In Chapter 3, the initial coordination chemistry of the redox-active N,N’ -bis(2,6- 2- diisopropylphenyl)-o-phenylenediamido ligand (L ) was investigated. Li 2L(THF)3 reacts with iron(II) sources in toluene to yield LFe(η6-toluene). DFT, NMR, and X-ray data indicate that L2- 1- 6 oxidized to L in this transformation. [FeL(η -toluene)] reacts with CO to generate [FeL(CO) 3], - 0 with concomitant oxidation of L to L . Two equivalents of Li 2L react with both MoCl 4(THF)2 and VCl 2(tmeda) 2 yielding trimetallic sandwich compounds. ii In Chapter 4, reactivity of Pb(II) and Sn(II) complexes of L 2- was investigated. [PbL] and [SnL] react with mesityl azide in analogous C-H activations in which L 2- behaves as an actor ligand. 2- [PbL] forms a Lewis pair with ONMe 3, demonstrating the behaviour of L as an ancillary ligand. [SnL] reacts with AgOTf to yield [SnL(OTf)], demonstrating the ligand’s redox activity as L 2- is oxidized to L -. [SnL(OTf)] is a paramagnetic stannylene, a type of compound which has been previously observed in situ , but hitherto has not been isolated. In Chapter 5, the coordination of different o-phenylenediamido sources towards [TaMe 3Cl 2] was explored. The opda framework acted as a reducing agent, as a sponsor of heterodinuclear complexes, or as a robust ancillary ligand. The use of K 2L provided access to [TaLMe 3]. The reactivity of its methyl ligands was studied; notably, UV irradiation causes formal loss of methyl radical to yield dimeric [LTaMe 2]2. iii Acknowledgments Thanks to my PhD supervisor, Professor Datong Song, for giving me cool projects to work on and for letting me pursue what I was interested in. His guidance helped me immeasurably. I am truly thankful for his ongoing support. Thanks to the various agencies that gave me money to do research, including the government of Ontario, University of Toronto, and the Graduate Student Endowment Fund. Thanks to my committee members Professors Bob Morris and Ulrich Fekl, and exam committee members Professors Sophie Rousseaux and Frédéric-Georges Fontaine. Thanks to Prof. Yang Li for hosting me in a research stint at Chongqing University; my time in his laboratory was one of the highlights of my PhD. Thanks to Prof. Parisa Mehrkhodavandi, Prof. Laurel Schafer, and Insun Yu for mentoring me during my undergraduate experience at UBC, and for helping me get “it” together. Thanks to all the departmental staff that assisted me, especially Anna Liza Villavelez, Ken Greaves, John Ford, Jack O’Donnell, Tim Burrows, Darcy Burns, Jack Sheng, Dmitry Pichugin, Sergiy Nokhrin, Rose Balazs, Jack Jackiewicz, and Alan Lough. Thanks to Song group members past and present for being great to work with, especially Runyu Tan, Yu Li, Tao Bai, Shaolong Gong, Xiaofei Li, Kim Osten, Rhys Batcup, Tara Cho, Celia Gendron-Herndon, Adam Pantaleo, Yanxin Yang, Charlie Kivi, Walter Liang, Fred Chiu, Ellen Yan, and Daniel Dalessandro. Thanks to Yasser Hassan, a class act, a tenacious, enterprising scientist. It was a privilege to collaborate with you. To the undergraduates I mentored . .you’re welcome! Maotong Xu, Xhoana Gjergji, Pavel Zatsepin, William Kim, Menandro Cruz, and Ben Tsui. Thanks for working with me, I know I benefitted immensely from our time together. Thanks to my parents Doug and Karen Janes. Thanks for your love and support, for the opportunities you provided, and for the best upbringing I can imagine. Thanks to my brother iv Andrew Janes; you’re the nuttiest. Thanks to my aunt Sandra Robertson for being an impossibly great listener, and my uncle Al Robertson for making me explain my research when I came home for holidays. Thanks to my grandma Shirley Matheson for applying the pressure I needed to wrap up this degree. Thanks to my special lady, my love, my sweetie, Laura Brown. v Table of Contents Acknowledgments.......................................................................................................................... iv Table of Contents ........................................................................................................................... vi List of Tables ................................................................................................................................. xi List of Figures ............................................................................................................................... xii List of Schemes ........................................................................................................................... xvii List of Abbreviations and Symbols................................................................................................xx 1 Introduction .................................................................................................................................1 1.1 CO 2 activation ......................................................................................................................1 1.1.1 Metal-free CO 2 activation ........................................................................................1 1.1.2 Metal-Ligand Cooperation for CO 2 activation ........................................................3 1.1.3 Other stoichiometric reactivity of CO 2 ....................................................................5 1.1.4 Insertions of CO 2......................................................................................................6 1.2 Redox-active ligands ............................................................................................................7 1.2.1 Redox-active vs. noninnocent ..................................................................................8 1.2.2 Pyridine diimine ligands ..........................................................................................8 1.2.3 Multielectron redox chemistry of d 0 tantalum complexes .......................................9 1.2.4 Negishi-type coupling using redox active ligands on Co ......................................10 1.3 N2 activation.......................................................................................................................11 1.4 NN chelate actor ligands ....................................................................................................13 1.4.1 4,5-diazafluorene ...................................................................................................14 1.4.2 o-phenylenediamine ...............................................................................................16 1.5 Scope and objectives ..........................................................................................................17 1.6 References ..........................................................................................................................20 2 Chapter 2 Insertion of CO 2 into the carbon—boron bond of a boronic ester ligand ................23 vi 2.1 Abstract ..............................................................................................................................23 2.2 Introduction ........................................................................................................................23 2.3 Results and Discussion ......................................................................................................25 2.4 Conclusion .........................................................................................................................47 2.5 Experimental ......................................................................................................................48 2.5.1 General procedures. ...............................................................................................48 2.5.2 Synthesis of 1a .......................................................................................................49 2.5.3 Synthesis of 2a .......................................................................................................49 2.5.4 Synthesis of 3a .......................................................................................................50 2.5.5 Synthesis of EtZn(Mes 2nacnac) .............................................................................51 2.5.6 Synthesis of 1b .......................................................................................................51 2.5.7 Synthesis of 2b .......................................................................................................52 2.5.8 Synthesis
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