Overview
- Nominated as an outstanding PhD thesis by Peking University
- Combines ion mobility mass spectrometry and computational chemistry to investigate reaction mechanisms in catalysis
- Provides mechanistic insights for a broad range of important C-H activation reactions
- Establishes a universal chirality-relay model for Pd/mono-N-protected amino acid (MPAA)-catalyzed asymmetric C-H activation reactions
- Includes supplementary material: sn.pub/extras
Part of the book series: Springer Theses (Springer Theses)
Access this book
Tax calculation will be finalised at checkout
Other ways to access
Table of contents (5 chapters)
-
Front Matter
Keywords
About this book
This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction.
The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.
Authors and Affiliations
Bibliographic Information
Book Title: Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods
Authors: Gui-Juan Cheng
Series Title: Springer Theses
DOI: https://doi.org/10.1007/978-981-10-4521-9
Publisher: Springer Singapore
eBook Packages: Chemistry and Materials Science, Chemistry and Material Science (R0)
Copyright Information: Springer Nature Singapore Pte Ltd. 2017
Hardcover ISBN: 978-981-10-4520-2Published: 26 June 2017
Softcover ISBN: 978-981-13-5157-0Published: 12 December 2018
eBook ISBN: 978-981-10-4521-9Published: 07 June 2017
Series ISSN: 2190-5053
Series E-ISSN: 2190-5061
Edition Number: 1
Number of Pages: XVII, 126
Number of Illustrations: 18 b/w illustrations, 77 illustrations in colour
Topics: Theoretical and Computational Chemistry, Organometallic Chemistry, Catalysis, Mass Spectrometry