Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations

The thesis is divided into two parts. Part I: Synthesis, Characterization and Reactivity studies on Ir(III) and Ru(IV) Complexes with Sulfur Ligands. Investigations into the reactivity of [Cp*Ir(η3-C4H8S3)] (1) in the role of metallo-ligand towards other organometallic species and alkylating reagent...

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Main Author: Xu, Chang
Other Authors: Pullarkat A. Sumod
Format: Thesis
Language:English
Published: 2012
Subjects:
Online Access:https://hdl.handle.net/10356/50629
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author Xu, Chang
author2 Pullarkat A. Sumod
author_facet Pullarkat A. Sumod
Xu, Chang
author_sort Xu, Chang
collection NTU
description The thesis is divided into two parts. Part I: Synthesis, Characterization and Reactivity studies on Ir(III) and Ru(IV) Complexes with Sulfur Ligands. Investigations into the reactivity of [Cp*Ir(η3-C4H8S3)] (1) in the role of metallo-ligand towards other organometallic species and alkylating reagents will be discussed. The catalytic potential of 1 in low catalyst loading and additive free β-alkylation reactions involving alcohols and in a highly selective imine synthesis protocol (via catalytic N-alkylation of amines with alcohols) will be presented. Results from the reactivity studies of [{(η3:η3-C10H16)Ru(-Cl)Cl}2] with dithiuram disulfides [R2NC(S)S-]2 (R = Me, iPr) and thiuram monosulfide will also be discussed. Part II: Catalytic Applications of Ru and Pd Metallacycles in C-C and C-P Bond Formations. A novel ruthenacycle catalyzed one-pot β-alkylation of alcohols which tolerates non-traditional substrates was developed. An efficient one-pot synthesis of 2,3-substituted indoles via domino cyclization/alkylation reaction of 2-alkynylanilines with allylic alcohols was also investigated. A highly enantio-selective asymmetric synthesis of chiral monophosphine ferrocenyl (MOPF) ligands and diester functionalized tertiary phosphines will also be discussed. Mechanistic insights from the aforementioned catalytic protocols will be presented.
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spelling ntu-10356/506292023-02-28T23:44:44Z Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations Xu, Chang Pullarkat A. Sumod School of Physical and Mathematical Sciences DRNTU::Science::Chemistry The thesis is divided into two parts. Part I: Synthesis, Characterization and Reactivity studies on Ir(III) and Ru(IV) Complexes with Sulfur Ligands. Investigations into the reactivity of [Cp*Ir(η3-C4H8S3)] (1) in the role of metallo-ligand towards other organometallic species and alkylating reagents will be discussed. The catalytic potential of 1 in low catalyst loading and additive free β-alkylation reactions involving alcohols and in a highly selective imine synthesis protocol (via catalytic N-alkylation of amines with alcohols) will be presented. Results from the reactivity studies of [{(η3:η3-C10H16)Ru(-Cl)Cl}2] with dithiuram disulfides [R2NC(S)S-]2 (R = Me, iPr) and thiuram monosulfide will also be discussed. Part II: Catalytic Applications of Ru and Pd Metallacycles in C-C and C-P Bond Formations. A novel ruthenacycle catalyzed one-pot β-alkylation of alcohols which tolerates non-traditional substrates was developed. An efficient one-pot synthesis of 2,3-substituted indoles via domino cyclization/alkylation reaction of 2-alkynylanilines with allylic alcohols was also investigated. A highly enantio-selective asymmetric synthesis of chiral monophosphine ferrocenyl (MOPF) ligands and diester functionalized tertiary phosphines will also be discussed. Mechanistic insights from the aforementioned catalytic protocols will be presented. DOCTOR OF PHILOSOPHY (SPMS) 2012-08-08T01:25:20Z 2012-08-08T01:25:20Z 2012 2012 Thesis Xu, C. (2012). Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/50629 10.32657/10356/50629 en 150 p. application/pdf
spellingShingle DRNTU::Science::Chemistry
Xu, Chang
Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title_full Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title_fullStr Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title_full_unstemmed Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title_short Part I: Synthesis, characterization and reactivity studies on Ir(III) and Ru(IV) complexes with sulfur ligands. Part II: Catalytic applications of Ru and Pd metallacycles in C-C and C-P bond formations
title_sort part i synthesis characterization and reactivity studies on ir iii and ru iv complexes with sulfur ligands part ii catalytic applications of ru and pd metallacycles in c c and c p bond formations
topic DRNTU::Science::Chemistry
url https://hdl.handle.net/10356/50629
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