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Design, synthesis and mechanistic studies of iron-TAML catalytic activators of hydrogen peroxide and a new activation chemistry of dioxygen by iron.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Design, synthesis and mechanistic studies of iron-TAML catalytic activators of hydrogen peroxide and a new activation chemistry of dioxygen by iron./
作者:	Ghosh, Anindya.
面頁冊數:	1 online resource (199 pages)
附註:	Source: Dissertations Abstracts International, Volume: 66-09, Section: B.
Contained By:	Dissertations Abstracts International66-09B.
標題:	Chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3146408click for full text (PQDT)
ISBN:	9780496075539

Design, synthesis and mechanistic studies of iron-TAML catalytic activators of hydrogen peroxide and a new activation chemistry of dioxygen by iron.
Ghosh, Anindya.

Design, synthesis and mechanistic studies of iron-TAML catalytic activators of hydrogen peroxide and a new activation chemistry of dioxygen by iron. - 1 online resource (199 pages)

Source: Dissertations Abstracts International, Volume: 66-09, Section: B.

Thesis (Ph.D.)--Carnegie Mellon University, 2004.

Includes bibliographical references

The Collins group has designed, synthesized, and characterized Fe(III)-tetraamido macrocycle (Fe(III)-TAML) catalysts capable of activating hydrogen peroxide for technologically prevalent oxidation chemistry. As discussed in Chapter 2, a new synthetic method has been developed resulting in higher yields, time savings, less environmental impact, and a more economical process. Chapter 3 describes the chemistry of various Fe(III)-TAML catalysts in aqueous solution. Detailed kinetic studies of the acid-induced demetallation of Fe(III)-TAMLs, their speciation and acid-base equilibria, and binding by anionic ligands such as chloride have been performed using several spectroscopic methods such as EPR, UV/Vis and X-ray crystallography. Chapter 4 describes a detailed kinetic and mechanistic investigation of the catalase and peroxidase like activity of Fe(III)-TAMLs. The objectives of this study include, understanding the major kinetic features of catalysis by the Fe(III)-TAML activators; estimation of the absolute reactivity of the Fe(III)-TAML activators in order to compare their activity to the relevant catalase and peroxidase enzymes, and to more fully understand the little known catalytic mechanism of the catalase-peroxidase enzymes by studying Fe(III)-TAML activators as their functioning mimetics. Chapter 5 describes our recent advancements towards the potential activation of dioxygen by Fe(III)-TAMLs. The 5-coordinated tetraphenylphosphonium salts of electron-rich Fe(III)-TAML complexes with an axial aqua ligand react rapidly with O2, under ambient conditions in methylene chloride, or other weakly coordinating solvents, to render μ-oxo-bridged diiron(IV) complexes (2). Isotopic labeling experiments with 18O 2 and H218O have established that the bridging oxygen atom of 2 derives from an O2 molecule. Autoxidation was shown not to be involved in the formation of 2. Chapter 6 summarizes our initial efforts in the application of Fe(III)-TAMLs for green syntheses such as hydrocarbon hydroxylation and epoxidation of alkenes. The results indicate that Fe(III)-TAMLs are capable of hydroxylating benzene and toluene, along with epoxidize alkenes like styrene, stilbene, and cyclooctene. These results also indicate that the electronic properties of the Fe(III)-TAMLs may play a significant role in controlling the reactivity and selectivity of substrate oxidation. Therefore, various Fe(III)-TAML activators, containing electron-withdrawing and electron-releasing groups, should be tested to achieve higher yields under optimized experimental conditions. (Abstract shortened by UMI.).

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9780496075539Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

DioxygenIndex Terms--Genre/Form:

542853
Electronic books.

Design, synthesis and mechanistic studies of iron-TAML catalytic activators of hydrogen peroxide and a new activation chemistry of dioxygen by iron.
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502 $a Thesis (Ph.D.)--Carnegie Mellon University, 2004.
504 $a Includes bibliographical references
520 $a The Collins group has designed, synthesized, and characterized Fe(III)-tetraamido macrocycle (Fe(III)-TAML) catalysts capable of activating hydrogen peroxide for technologically prevalent oxidation chemistry. As discussed in Chapter 2, a new synthetic method has been developed resulting in higher yields, time savings, less environmental impact, and a more economical process. Chapter 3 describes the chemistry of various Fe(III)-TAML catalysts in aqueous solution. Detailed kinetic studies of the acid-induced demetallation of Fe(III)-TAMLs, their speciation and acid-base equilibria, and binding by anionic ligands such as chloride have been performed using several spectroscopic methods such as EPR, UV/Vis and X-ray crystallography. Chapter 4 describes a detailed kinetic and mechanistic investigation of the catalase and peroxidase like activity of Fe(III)-TAMLs. The objectives of this study include, understanding the major kinetic features of catalysis by the Fe(III)-TAML activators; estimation of the absolute reactivity of the Fe(III)-TAML activators in order to compare their activity to the relevant catalase and peroxidase enzymes, and to more fully understand the little known catalytic mechanism of the catalase-peroxidase enzymes by studying Fe(III)-TAML activators as their functioning mimetics. Chapter 5 describes our recent advancements towards the potential activation of dioxygen by Fe(III)-TAMLs. The 5-coordinated tetraphenylphosphonium salts of electron-rich Fe(III)-TAML complexes with an axial aqua ligand react rapidly with O2, under ambient conditions in methylene chloride, or other weakly coordinating solvents, to render μ-oxo-bridged diiron(IV) complexes (2). Isotopic labeling experiments with 18O 2 and H218O have established that the bridging oxygen atom of 2 derives from an O2 molecule. Autoxidation was shown not to be involved in the formation of 2. Chapter 6 summarizes our initial efforts in the application of Fe(III)-TAMLs for green syntheses such as hydrocarbon hydroxylation and epoxidation of alkenes. The results indicate that Fe(III)-TAMLs are capable of hydroxylating benzene and toluene, along with epoxidize alkenes like styrene, stilbene, and cyclooctene. These results also indicate that the electronic properties of the Fe(III)-TAMLs may play a significant role in controlling the reactivity and selectivity of substrate oxidation. Therefore, various Fe(III)-TAML activators, containing electron-withdrawing and electron-releasing groups, should be tested to achieve higher yields under optimized experimental conditions. (Abstract shortened by UMI.).
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