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Preparation and Characterization of ...

Goldberg, Jonathan M.

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Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation./
Author:	Goldberg, Jonathan M.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2017,
Description:	182 p.
Notes:	Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.
Contained By:	Dissertation Abstracts International78-08B(E).
Subject:	Inorganic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10257671
ISBN:	9781369693560

Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation.
Goldberg, Jonathan M.

Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation. - Ann Arbor : ProQuest Dissertations & Theses, 2017 - 182 p.

Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.

Thesis (Ph.D.)--University of Washington, 2017.

This thesis describes the fundamental organometallic reactivity of iridium pincer complexes and their applications to glycerol deoxygenation catalysis. These investigations provide support for each step of a previously proposed glycerol deoxygenation mechanism. Chapter 1 outlines the motivations for this work, specifically the goal of using biomass as a chemical feedstock over more common petroleum-based sources. A discussion of the importance of transforming glycerol to higher value products, such as 1,3-propanediol, is discussed. Chapter 2 describes investigations into the importance of pincer ligand steric factors on the coordination chemistry of the iridium metal center. Full characterization of a five-coordinate iridium-hydride complex is presented; this species was previously proposed to be a catalyst resting state for glycerol deoxygenation. Chapter 3 investigates hydrogen addition to R4(POCOP)Ir(CO) [R4POCOP = kappa3-C6H3-2,6-(OPR2)2 for R = tBu, iPr] and R4(PCP)Ir(CO) [R4(PCP) = kappa3-C6H3-2,6-(CH 2PR2)2 for R = tBu, iPr] to give cis- and/or trans-dihydride complexes. Two mechanisms of hydrogen addition are presented (concerted oxidative addition and proton-catalyzed addition); the mechanism of hydrogen addition is dependent on the steric environment at the metal center. Chapter 4 presents spectroscopic evidence for two new iridium-dihydrogen complexes only stable under high pressures of hydrogen (40--80 atm) and low temperatures. Furthermore, iridium-catalyzed isotope exchange between H2 and CD3OD is presented and its potential implications in supporting the glycerol deoxygenation mechanism. Chapter 5 outlines a fundamental reaction of oxidative addition of iodine to (tBu)4(POCOP)Ir(CO) complexes. Characterization of a cationic monoiodo iridium carbonyl complex as a potential oxidative addition intermediate is presented.

ISBN: 9781369693560Subjects--Topical Terms:

3173556
Inorganic chemistry.

Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation.
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245 1 0 $a Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation.
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300 $a 182 p.
500 $a Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.
500 $a Advisers: D. Michael Heinekey; Karen I. Goldberg.
502 $a Thesis (Ph.D.)--University of Washington, 2017.
520 $a This thesis describes the fundamental organometallic reactivity of iridium pincer complexes and their applications to glycerol deoxygenation catalysis. These investigations provide support for each step of a previously proposed glycerol deoxygenation mechanism. Chapter 1 outlines the motivations for this work, specifically the goal of using biomass as a chemical feedstock over more common petroleum-based sources. A discussion of the importance of transforming glycerol to higher value products, such as 1,3-propanediol, is discussed. Chapter 2 describes investigations into the importance of pincer ligand steric factors on the coordination chemistry of the iridium metal center. Full characterization of a five-coordinate iridium-hydride complex is presented; this species was previously proposed to be a catalyst resting state for glycerol deoxygenation. Chapter 3 investigates hydrogen addition to R4(POCOP)Ir(CO) [R4POCOP = kappa3-C6H3-2,6-(OPR2)2 for R = tBu, iPr] and R4(PCP)Ir(CO) [R4(PCP) = kappa3-C6H3-2,6-(CH 2PR2)2 for R = tBu, iPr] to give cis- and/or trans-dihydride complexes. Two mechanisms of hydrogen addition are presented (concerted oxidative addition and proton-catalyzed addition); the mechanism of hydrogen addition is dependent on the steric environment at the metal center. Chapter 4 presents spectroscopic evidence for two new iridium-dihydrogen complexes only stable under high pressures of hydrogen (40--80 atm) and low temperatures. Furthermore, iridium-catalyzed isotope exchange between H2 and CD3OD is presented and its potential implications in supporting the glycerol deoxygenation mechanism. Chapter 5 outlines a fundamental reaction of oxidative addition of iodine to (tBu)4(POCOP)Ir(CO) complexes. Characterization of a cationic monoiodo iridium carbonyl complex as a potential oxidative addition intermediate is presented.
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