nach oben

2016 | Buch

Kapitel lesen Erstes Kapitel lesen

Group 2 Mediated Dehydrocoupling

verfasst von: David J. Liptrot

Verlag: Springer International Publishing

Buchreihe : Springer Theses

Enthalten in: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik" , Springer Professional "Wirtschaft"

Einloggen, um Zugang zu erhalten

Über dieses Buch

This book presents an in-depth study into the utility of σ-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner. Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with σ-bond metathesis allows a novel hydrogen release from silanes.

Inhaltsverzeichnis

Frontmatter

Chapter 1. Introduction

Abstract

The transition metals are well known for their extensive catalytic chemistry (e.g. Pd, Ru, Ir) and a vast range of transformations are accessible utilising these elements.

David J. Liptrot

Chapter 2. Group 1-Group 2 Bimetallic Alkyls and Hydrides

Abstract

Main group heterobimetallic compounds are extremely common and encompass a variety of simple salts and cluster types.

David J. Liptrot

Chapter 3. Silicon–Nitrogen Dehydrocoupling

Abstract

Silicon–nitrogen coupling is a reaction of significant interest. Compounds containing Si–N bonds are utilised as silylating agents [1], bases [2], ligands and ceramic precursors [3] and furthermore silanes act as protecting groups for amides, and vice versa [4]. Current synthetic routes to these compounds rely on the atom uneconomical aminolysis of chlorosilanes yielding the desired product and HCl, which creates highly acidic reaction conditions, reducing functional group tolerance and acts as a waste stream [5].

David J. Liptrot

Chapter 4. Boron–Nitrogen Dehydrocoupling

Abstract

Beyond the dehydrocoupling of Group 14 elements with protic amines, the extension of such reactivity to hydridic reagents from Group 13 is attractive, most notably boranes yielding aminoboranes.

David J. Liptrot

Chapter 5. Single Electron Transfer Steps in Group 2 Catalysis

Abstract

The stable nitroxyl radical, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy), has attracted widespread interest since its first synthesis in 1960.

David J. Liptrot

Chapter 6. Summary

Abstract

In summary, this thesis describes a variety of investigations into the utility of Group 2-mediated σ-bond metathesis, both for synthetic stoichiometric reactions and, further, for catalytic dehydrocouplings.

David J. Liptrot

Chapter 7. Future Work

Abstract

Although extensive studies are herein described, a number of aspects of future work are necessary in order to gain greater insight into both Group 2 mediated dehydrocoupling, the synthetic utility of σ-bond metathesis in the synthesis of novel s-block compounds and the use of single electron transfer steps in Group 2 mediated reactivity.

David J. Liptrot

Backmatter

Titel: Group 2 Mediated Dehydrocoupling
verfasst von: David J. Liptrot
Verlag: Springer International Publishing
Electronic ISBN: 978-3-319-21036-0
Print ISBN: 978-3-319-21035-3
DOI: https://doi.org/10.1007/978-3-319-21036-0

Premium Partner

Marktübersichten

Die im Laufe eines Jahres in der „adhäsion“ veröffentlichten Marktübersichten helfen Anwendern verschiedenster Branchen, sich einen gezielten Überblick über Lieferantenangebote zu verschaffen.

Zur Marktübersicht