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Dissertation (Hosein Tafazolian).pdf (3.45 MB)

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Hydroamination and Hydrosilylation Catalyzed by Cationic Palladium- and Nickel(allyl) Complexes Supported by 3-Iminophosphine Ligands

Tafazolian, Hosein
http://rave.ohiolink.edu/etdc/view?acc_num=toledo1473397460390363

Abstract Details

2016, Doctor of Philosophy, University of Toledo, Chemistry.
Chapter 1. A brief introduction to organometallic chemistry and catalysis is presented to explain the basics of the field to the reader. A few examples of catalysis, mainly hydroamination and hydrosilylation, and their mechanisms are presented. The significance of ligands in catalysis is also discussed. Chapter 2. Six new 3-iminophosphine ligands and their cationic (allyl)palladium complexes were synthesized. These catalytically active palladium complexes were utilized in the hydroamination of cyclohexylallene with secondary amines in order to better understand the mechanism of this hydroamination reaction. The kinetics of the reaction were also studied with the help of time-resolved proton NMR spectroscopy, as well as deuterium labeling experiments. Chapter 3. Four new [(3-iminophosphine)nickel(allyl)]OTf complexes were synthesized and characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. Equimolar reactions of these new complexes with secondary amines provided useful information on the activation of these complexes in the presence of secondary amines. They also catalyzed the hydroamination of terminal allenes with secondary amines to produce allylamines in moderate to high yields, which were then characterized by proton and carbon NMR spectroscopy and high resolution mass spectrometry. Chapter 4. A previously synthesized [(3-iminophosphine)palladium(allyl)]OTf complex was found to be an efficient catalyst for the hydrosilylation of allenes with a wide range of hydrosilanes. Several new allyl- and vinylsilanes were synthesized catalytically and fully characterized. The observed regioselectivity and a double labeled H/D experiment resolved the mechanism of the reaction while also explaining its regioselectivity. Chapter 5. Various cationic palladium and nickel complexes were investigated in the hydrosilylation of imines, ketones, and alkynes. Several new allylamine, silylether and vinylsilane compounds were formed in this study and characterized. Substrate scope and mechanisms of the catalytic reactions are discussed.
Joseph Schmidt (Committee Chair)
Mark Mason (Committee Member)
Steven Sucheck (Committee Member)
John-David Smith (Committee Member)
195 p.
Chemistry
Hydroamination; hydrosilylation; palladium; nickel; 3-iminophosphine ligands

Recommended Citations

Citations

  • Tafazolian, H. (2016). Hydroamination and Hydrosilylation Catalyzed by Cationic Palladium- and Nickel(allyl) Complexes Supported by 3-Iminophosphine Ligands [Doctoral dissertation, University of Toledo]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1473397460390363

    APA Style (7th edition)

  • Tafazolian, Hosein. Hydroamination and Hydrosilylation Catalyzed by Cationic Palladium- and Nickel(allyl) Complexes Supported by 3-Iminophosphine Ligands. 2016. University of Toledo, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=toledo1473397460390363.

    MLA Style (8th edition)

  • Tafazolian, Hosein. "Hydroamination and Hydrosilylation Catalyzed by Cationic Palladium- and Nickel(allyl) Complexes Supported by 3-Iminophosphine Ligands." Doctoral dissertation, University of Toledo, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1473397460390363

    Chicago Manual of Style (17th edition)

toledo1473397460390363
679
© 2016, all rights reserved.
This open access ETD is published by University of Toledo and OhioLINK.