Yu Lan - Computational Methods in Organometallic Catalysis

1 Cover

2 Title Page Computational Methods in Organometallic Catalysis From Elementary Reactions to Mechanisms Yu Lan

3 Copyright Author Prof. Yu Lan Zhengzhou University Green Catalysis Center, and College of Chemistry 450001 Zhengzhou China Cover Image : ©Vikks/Shutterstock All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing‐in‐Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at < http://dnb.d-nb.de >. © 2021 WILEY‐VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Print ISBN: 978‐3‐527‐34601‐1 ePDF ISBN: 978‐3‐527‐34605‐9 ePub ISBN: 978‐3‐527‐34603‐5 oBook ISBN: 978‐3‐527‐34602‐8

4 Foreword

5 Preface

6 Part I: Theoretical View of Organometallic Catalysis 1 Introduction of Computational Organometallic Chemistry 1.1 Overview of Organometallic Chemistry 1.2 Using Computational Tool to Study the Organometallic Chemistry Mechanism References 2 Computational Methods in Organometallic Chemistry2.1 Introduction of Computational Methods 2.2 Density Functional Theory (DFT) Methods 2.3 Basis Set and Its Application in Mechanism Studies 2.4 Solvent Effect 2.5 How to Choose a Method in Computational Organometallic Chemistry 2.6 Revealing a Mechanism for An Organometallic Reaction by Theoretical Calculations 2.7 Overview of Popular Computational Programs 2.8 The Limitation of Current Computational Methods References 3 Elementary Reactions in Organometallic Chemistry 3.1 General View of Elementary Reactions in Organometallic Chemistry 3.2 Coordination and Dissociation 3.3 Oxidative Addition 3.4 Reductive Elimination 3.5 Insertion 3.6 Elimination 3.7 Transmetallation 3.8 Metathesis References

7 Part II: On the Mechanism of Transition‐metal‐assisted Reactions 4 Theoretical Study of Ni‐Catalysis 4.1 Ni‐Mediated C—H Bond Activation 4.2 Ni‐Mediated C—Halogen Bond Cleavage 4.3 Ni‐Mediated C—O Bond Activation 4.4 Ni‐Mediated C—N Bond Cleavage 4.5 Ni‐Mediated C—C Bond Cleavage 4.6 Ni‐Mediated Unsaturated Bond Activation 4.7 Ni‐Mediated Cyclization References 5 Theoretical Study of Pd‐Catalysis 5.1 Pd‐Catalyzed Cross‐coupling Reactions 5.2 Pd‐Mediated C—Hetero Bond Formation 5.3 Pd‐Mediated C—H Activation Reactions 5.4 Pd‐Mediated Activation of Unsaturated Molecules 5.5 Allylic Pd Complex References 6 Theoretical Study of Pt‐Catalysis 6.1 Mechanism of Pt‐Catalyzed C—H Activation 6.2 Mechanism of Pt‐Catalyzed Alkyne Activation 6.3 Mechanism of Pt‐Catalyzed Alkene Activation References 7 Theoretical Study of Co‐Catalysis 7.1 Co‐Mediated C—H Bond Activation 7.2 Co‐Mediated Cycloadditions 7.3 Co‐Catalyzed Hydrogenation 7.4 Co‐Catalyzed Hydroformylation 7.5 Co‐Mediated Carbene Activation 7.6 Co‐Mediated Nitrene Activation References 8 Theoretical Study of Rh‐Catalysis 8.1 Rh‐Mediated C—H Activation Reactions 8.2 Rh‐Catalyzed C—C Bond Activations and Transformations 8.3 Rh‐Mediated C—Hetero Bond Activations 8.4 Rh‐Catalyzed Alkene Functionalizations 8.5 Rh‐Catalyzed Alkyne Functionalizations 8.6 Rh‐Catalyzed Addition Reactions of Carbonyl Compounds 8.7 Rh‐Catalyzed Carbene Transformations 8.8 Rh‐Catalyzed Nitrene Transformations 8.9 Rh‐Catalyzed Cycloadditions References 9 Theoretical Study of Ir‐Catalysis 9.1 Ir‐Catalyzed Hydrogenations 9.2 Ir‐Catalyzed Hydrofunctionalizations 9.3 Ir‐Catalyzed Borylations 9.4 Ir‐Catalyzed Aminations 9.5 Ir‐Catalyzed C—C Bond Coupling Reactions References 10 Theoretical Study of Fe‐Catalysis 10.1 Fe‐Mediated Oxidations 10.2 Fe‐Mediated Hydrogenations 10.3 Fe‐Mediated Hydrofunctionalizations 10.4 Fe‐Mediated Dehydrogenations 10.5 Fe‐Catalyzed Coupling Reactions References 11 Theoretical Study of Ru‐Catalysis 11.1 Ru‐Mediated C—H Bond Activation 11.2 Ru‐Catalyzed Hydrogenations 11.3 Ru‐Catalyzed Hydrofunctionalizations 11.4 Ru‐Mediated Dehydrogenations 11.5 Ru‐Catalyzed Cycloadditions 11.6 Ru‐Mediated Metathesis References 12 Theoretical Study of Mn‐Catalysis 12.1 Mn‐Mediated Oxidation of Alkanes 12.2 Mn‐Mediated C—H Activations 12.3 Mn‐Mediated Hydrogenations 12.4 Mn‐Mediated Dehydrogenations References 13 Theoretical Study of Cu‐Catalysis 13.1 Cu‐Mediated Ullmann Condensations 13.2 Cu‐Mediated Trifluoromethylations 13.3 Cu‐Mediated C—H Activations 13.4 Cu‐Mediated Alkyne Activations 13.5 Cu‐Mediated Carbene Transformations 13.6 Cu‐Mediated Nitrene Transformations 13.7 Cu‐Catalyzed Hydrofunctionalizations 13.8 Cu‐Catalyzed Borylations References 14 Theoretical Study of Ag‐Catalysis 14.1 Ag‐Mediated Carbene Complex Transformations 14.2 Ag‐Mediated Nitrene Transformations 14.3 Ag‐Mediated Silylene Transformations 14.4 Ag‐Mediated Alkyne Activations References 15 Theoretical Study of Au‐Catalysis 15.1 Au‐Mediated Alkyne Activations 15.2 Au‐mediated Alkene Activations 15.3 Au‐mediated Allene Activations 15.4 Au‐mediated Enyne Transformations References

8 Index

9 End User License Agreement

1 Chapter 2 Table 2.1 Properties of frequently used approaches for the dispersion correct... Table 2.2 Scaling behaviors of computational methods.

1 Chapter 1 Scheme 1.1 Cross‐coupling reactions with nucleophiles and electrophiles. Scheme 1.2 Some selected examples of nucleophiles. Scheme 1.3 A brief history of organometallic chemistry. Scheme 1.4 Revealing the reaction mechanism of organometallic catalysis. Scheme 1.5 The resonance structures of (Xantphos)Pd(CH 2NBn 2) +. Scheme 1.6 Mechanism of rhodium‐catalyzed coupling reaction of quinoline N ‐o... Scheme 1.7 Mechanism study of organometallic catalysis by density functional...

2 Chapter 2 Scheme 2.1 Jacob's ladder of density functionals. Scheme 2.2 The frequently used approaches for the dispersion correction of d... Scheme 2.3 The combination of Gaussian‐type orbitals (GTOs) for the construc...

3 Chapter 3 Scheme 3.1 The coordination of ligand onto metal. Scheme 3.2 Back‐donation bonds in metal‐η 2–alkene (a), metal‐η 2–dihydrogen (... Figure 3.1 The free‐energy profiles for the coordination of phosphine onto p... Figure 3.2 The free‐energy profiles for the coordination of acetylene onto O... Figure 3.3 The free‐energy profiles for the moving of Cr(CO) 3on a polycycli... Figure 3.4 The relative free energies of Ni–carbene complexes. The free ener... Figure 3.5 The free‐energy profiles for the dissociation of phosphine ligand... Scheme 3.3 Possible pathways for the ligand exchange. Figure 3.6 The mechanism of ligand exchange in the regeneration of Pd‐cataly... Figure 3.7 The free‐energy profiles for the cis‐/trans‐isomerization of Cl 2P.