Yu Lan - Computational Methods in Organometallic Catalysis

578 583

579 584

580 585

581 586

582 587

583 588

584 589

585 590

586 591

587 592

588 593

589 594

590 595

591 597

592 598

593 599

594 600

595 601

596 602

597 603

598 604

599 605

600 606

601 607

602 608

603 609

604 610

605 611

606 612

607 613

608 614

609 615

610 616

611 617

612 618

613 619

614 620

615 621

616 622

617 623

618 624

619 625

620 626

621 627

622 629

623 630

624 631

625 632

626 633

627 634

628 635

629 636

630 637

631 638

632 639

633 640

634 641

635 642

636 643

637 644

638 645

639 646

640 647

641 648

642 649

Yu Lan

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‐VCHare 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 DataA catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche NationalbibliothekThe 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

Computational chemistry began in the 1940s with the earliest electronic computers and drastic approximations to the Schrödinger equation, such as Hückel molecular orbital theory. Since the 1960s, the possibilities of doing quantum mechanics calculations on large systems containing metals, indeed to study the heart of organometallic chemistry, began with the Mulliken–Wolfsberg–Helmholtz approach and then Roald Hoffmann's Extended Hückel Theory (EHT) in the 1950s and 1960s. While an amazingly useful method, EHT is really only of qualitative value. But actually what we need is a conceptual framework that is useful even today.

The 1960s saw remarkable advances in methods, approximations, and the beginnings of the flowering of computers for chemical calculations. The dawn of the modern hybrid density functional theory in the mid‐1990s, borrowing exact exchange from wavefunction theory, made it possible to begin the quantitative calculations of structure, mechanics, and mechanisms, including the incredibly useful organometallic reactions. Both Ru and Mo catalysts for olefin metathesis, and Pd catalysis for cross‐coupling reactions, have led to Nobel prizes for their discoverers.

Yu Lan has now written an introduction, a guide, a masterwork about quantum mechanical studies of organometallic reaction mechanisms. He is ideally equipped to write such a book, already doing outstanding work in the field as a student and postdoc, and becoming a leader in the field in his independent career. He has also trained many young experts in the field, and his influence will spread further from their achievements and through this book.

The book includes a historical introduction to organometallic chemistry, a survey of mechanisms, and an extensive introduction to quantum mechanical computational methods, especially density functional theory, as well as programs for quantum chemical calculations.

The description of organometallic structures and mechanisms is peppered with numerous calculations from the Lan group with relatively accurate density functionals. Part 2, the bulk of this book, is organized with a chapter for each of the most important metals used in organometallic chemistry: Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Mn, Cu, Ag, and Au. The computational studies of the reactions of complexes of each of these metals are reviewed with great insights into mechanisms using computations.

The book will be a boon to organometallic chemists and computational chemists involved in the study of organometallic reactions. While a number of books on organometallic chemistry mechanisms are available, this is THE book describing the methods for computation and analysis of organometallic reactions using modern quantum mechanical methods.

29 August 2020

Kendall N. Houk

A long time ago, when I first came into contact with science, I was fascinated by the unique charm of organic chemistry. The tetravalent carbon atoms and their tetrahedral structures impressed me with elegant simplicity. Through the broken and formation of covalent bonds, various new molecules that possess unique properties could be generated. By manipulating the reaction conditions, catalysts, and ligands in organic reactions, chemists can effectively synthesize plenty of complex natural product molecules and pharmaceutical molecules in high regioselectivity and enantioselectivity. When I was a teenager, I took every organic chemical reaction as a puzzle, and the reaction mechanism is like the answer to the puzzle. In this way, I found great pleasure in thinking about the mechanism of organic reactions. The development of organic chemistry also requires a comprehensive mechanistic understanding. Generally, a significant amount of information about reaction mechanisms could be obtained by experimental techniques. However, the experimental mechanistic study mainly focuses on the macroscopically observed experimental phenomena. Therefore, in many cases, pure experimental observation is not sufficient for revealing the complete reaction pathway and clarifying the origin of selectivity. During my doctoral study at Peking University, I was fortunate to work with my supervisor Professor Yun‐Dong Wu, from whom I learned how to use computational chemistry to investigate the organic reaction mechanisms. Theoretical calculations based on quantum mechanics, especially the density functional theory calculation, have constituted the most powerful tool for mechanistic study due to the development of supercomputer, computational theory, and corresponding software.

In the past several decades, one of the most important advances in organic chemistry has been the introduction of transition metal catalysts to organic synthesis. Transition metal species can react with organic compounds to generate intermediates that contain carbon–metal bonds. Subsequent conversion of these organometallic intermediates could enrich the synthetic approach toward new molecules. Different from organocatalysis, the organometallic catalysis usually goes through multiple steps and complicated catalytic cycles, which originated from the complex bonding pattern of organometallic catalysts and the variation of valance state of the central metal species. Thus, the utilization of theoretical calculation for understanding the reaction mechanism is imperative for the development of organic chemistry. My post‐doctoral research with Professor K. N. Houk was working with experimental chemists to explore the mechanism of organometallic reactions through the collaboration of theoretical calculation with experimental study. The promotion of theoretical study on experimental development could be summarized into “3D,” i.e. description, design, and direction. Based on the data obtained from experimental study, detailed descriptions of the organometallic reaction mechanisms could be fulfilled using theoretical calculation. The mechanistic study then provides further theoretical guidance for the rational design of new reactions, which points out the direction of experimental development.