332 Topics in Current Chemistry

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1 332 Topics in Current Chemistry Editorial Board: K.N. Houk, Los Angeles, CA, USA C.A. Hunter, Sheffield, UK M.J. Krische, Austin, TX, USA J.-M. Lehn, Strasbourg, France S.V. Ley, Cambridge, UK M. Olivucci, Siena, Italy J. Thiem, Hamburg, Germany M. Venturi, Bologna, Italy C.-H. Wong, Taipei, Taiwan H.N.C. Wong, Shatin, Hong Kong For further volumes:

2 Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage includes all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented. A description of the laboratory procedures involved is often useful to the reader. The coverage should not be exhaustive in data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Discussion of possible future research directions in the area is welcome. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students.

3 Gerhard Erker Douglas W. Stephan l Editors Frustrated Lewis Pairs I Uncovering and Understanding With contributions by K. Chernichenko H. Eckert G. Erker T.M. Gilbert S. Grimme F. Huang G. Kehr M. Leskelä H. Li G. Lu I. Pápai T. Repo B. Rieger T.A. Rokob B. Schirmer F. Schulz S. Schwendemann D.W. Stephan V. Sumerin Z.-X. Wang T. Wiegand L. Zhao

4 Editors Gerhard Erker Universität Münster Organisch-Chemisches Institut Münster Germany Douglas W. Stephan University of Toronto Department of Chemistry Toronto Canada ISSN ISSN (electronic) ISBN ISBN (ebook) DOI / Springer Heidelberg New York Dordrecht London Library of Congress Control Number: # Springer-Verlag Berlin Heidelberg 2013 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Duplication of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher s location, in its current version, and permission for use must always be obtained from Springer. Permissions for use may be obtained through RightsLink at the Copyright Clearance Center. Violations are liable to prosecution under the respective Copyright Law. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. While the advice and information in this book are believed to be true and accurate at the date of publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein. Printed on acid-free paper Springer is part of Springer Science+Business Media (

5 Preface Up until recently, our understanding of the chemistry resulting from the combination of Lewis acids and bases had not evolved much since Lewis time. In large part, the formation of Lewis acid base adducts drew little interest as these systems were with a few notable exceptions perceived as thermodynamic sinks. However in 2006, we learned that certain combinations of Lewis acids and Lewis bases could coexist in solution and provide the possibility of new, synergistic reactions in which both reagents participate in the activation of H 2. This archetypical reaction was first demonstrated with Lewis pairs in which adduct formation was sterically frustrated. Subsequently we learned that such frustrated Lewis pairs (FLPs) could also be derived from weak electronic attractions between the acid and base, and that this notion was not limited to group 13/15 combinations. The discovery of this seemingly simple concept led to the unprecedented application of FLPs in metal-free catalytic hydrogenations. Although the early developments were summarized in our 2010 review in Angewandte Chemie, the area has grown rapidly since then. Indeed, a number of creative and insightful contributions have broadened the range of FLP systems and led to dramatic developments including the activation of a variety of small molecules such as alkenes, alkynes, CO 2,N 2 O, and NO, among others. Theoretical studies have provided insight and understanding of this evolving area and exciting applications of FLPs in synthetic chemistry and catalysis continue have begun to emerge. These two volumes are a compilation of the state-of-the-art research concerning FLPs as of mid Over 20 researchers from around the globe have contributed chapters, detailing their inventive and astute contributions to this new and exciting area of the chemistry. These works cover a broad range of studies including synthetic chemistry, theoretical treatments, spectroscopic examinations, and catalytic applications. This breadth demonstrates the broad impact this work has had but furthermore speaks to the enormous potential for the future. It has been our great pleasure to have acted as editors for these volumes. It is our hope that this collection will not only highlight the amazing growth of this area in only a few years, but will moreover influence others to take up the task of exploring or exploiting FLPs in their own chemistry. Toronto, ON, Canada Münster, Germany Douglas W. Stephan Gerhard Erker v

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7 Contents Discovery of Frustrated Lewis Pairs: Intermolecular FLPs for Activation of Small Molecules... 1 Douglas W. Stephan Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features Gerald Kehr, Sina Schwendemann, and Gerhard Erker Frustrated Lewis Pair Mediated Hydrogenations Douglas W. Stephan and Gerhard Erker Amine-Borane Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation Victor Sumerin, Konstantin Chernichenko, Felix Schulz, Markku Leskelä, Bernhard Rieger, and Timo Repo Hydrogen Activation by Frustrated Lewis Pairs: Insights from Computational Studies Tibor András Rokob and Imre Pápai Quantum Chemistry of FLPs and Their Activation of Small Molecules: Methodological Aspects Birgitta Schirmer and Stefan Grimme Computational Design of Metal-Free Molecules for Activation of Small Molecules, Hydrogenation, and Hydroamination Zhi-Xiang Wang, Lili Zhao, Gang Lu, Haixia Li, and Fang Huang vii

8 viii Contents Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs Thomas M. Gilbert Solid-State NMR as a Spectroscopic Tool for Characterizing Phosphane Borane Frustrated Lewis Pairs Thomas Wiegand, Hellmut Eckert, and Stefan Grimme Index