Frustrated Lewis Pairs PDF
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Molecular Catalysis 2 Series Editors: Piet W. N. M. van Leeuwen · Carmen Claver · Nicholas Turner J. Chris Slootweg Andrew R. Jupp Editors Frustrated Lewis Pairs Molecular Catalysis Volume 2 Series Editors Piet W. N. M. van Leeuwen, LPCNO, Institut National des Sciences Appliqué, Toulouse, France Carmen Claver, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Tarragona, Spain NicholasTurner,SchoolofChemistry,UniversityofManchester,Manchester,UK Thisbookseriespublishes monographs andeditedbooksonallareas ofmolecular catalysis, including heterogeneous catalysis, nanocatalysis, biocatalysis, and homogeneous catalysis. The series also explores the interfaces between these areas. The individual volumes may discuss new developments in catalytic conversions, new catalysts, addressing existing reactions and new reactions regarded as desirable from a societal viewpoint. The focus on molecular insight requires an appropriate attention for synthesis of catalytic materials, their characterization by all spectroscopic and other means available, and theoretical studies of materials and reaction mechanisms, provided the topic is strongly interwoven with catalysis. Thus the series covers topics of interest toa wide range of academic and industrial chemists, and biochemists. More information about this series at http://www.springer.com/series/15831 J. Chris Slootweg Andrew R. Jupp (cid:129) Editors Frustrated Lewis Pairs 123 Editors J.Chris Slootweg AndrewR. Jupp Van‘tHoffInstituteforMolecularSciences Schoolof Chemistry University of Amsterdam University of Birmingham Amsterdam, TheNetherlands Edgbaston,UK ISSN 2522-5081 ISSN 2522-509X (electronic) Molecular Catalysis ISBN978-3-030-58887-8 ISBN978-3-030-58888-5 (eBook) https://doi.org/10.1007/978-3-030-58888-5 ©SpringerNatureSwitzerlandAG2021 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart 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 orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained hereinorforanyerrorsoromissionsthatmayhavebeenmade.Thepublisherremainsneutralwithregard tojurisdictionalclaimsinpublishedmapsandinstitutionalaffiliations. ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Frustrated Lewis pairs (FLPs) have been a key factor in the renaissance of main-groupchemistryinthepastfewdecades.Althoughitwasknownasearlyasthe 1940s that steric hindrance could preclude Lewis adduct formation, it was in 2006 thatDouglasStephanandhisteamshowedthatcombinationsofunquenchedLewis acidsandbasescouldbeusedtosplittheH–HbondinH .Thisdiscoverypavedthe 2 way for the FLPactivation of a wide range ofsmallmolecules, including environ- mentallyrelevantgasessuchascarbondioxide,sulfurdioxideandnitrogenoxides. More pertinent to the Molecular Catalysis series is their extraordinary ability to promote the catalytic hydrogenation of unsaturated organic substrates—a series of reactionsthatwerepreviouslythoughttobelimitedtotransitionmetalcompounds. Perhaps one of the greatest contributors to the growing popularity of research into frustrated Lewis pairs is their simplicity. There are innumerable combinations of Lewis acids and bases that can be trialled, and these have unlocked a fantastic array of reactions. A Web of Science search for the topic frustrated Lewis pairs shows just how quickly this field has burgeoned. The very first citation to a pub- lishedworkcontainingthistermwasin2007,andaswewritethisPrefaceonthe15 July 2020 there are almost 60,000 citations, with over 10,000 in 2019 alone. This book follows on from the two FLP titles that were published in 2013 (subtitled Uncovering and Understanding and Expanding the Scope), which were compiled andeditedbythetwoforefathersofFLPchemistry:DouglasStephan andGerhard Erker. We havebuilt on these foundations andattempted tocollate andsummarise the staggering progress made in the research area of FLP catalysis since those publications. We have by no means done this alone, and all the credit goes to the amazing researchers from around the globe who have contributed chapters to this book;wefeelitreallyprovidesasummaryofthestateoftheartinfrustratedLewis pair catalysis. Chapter1introducesthegeneraltopicofFLPcatalysisandprovidesthecontext fortheensuingchapters.Chapter2outlinesthephenomenalprogressthathasbeen made in recent years on asymmetric catalysis by FLPs. Chapters 3, 4 and 5 then cover specific transformations carried out by FLPs, specifically the reduction of carbon monoxide, the activation of C–H bonds and hydrogen activation, v vi Preface respectively. Chapter 6 surveys the different and novel boranes that have been developed as Lewis acids within FLP systems, and the new reactivity they can unlock. Chapter 7 explores the recent development of heterogeneous catalysts in FLP chemistry, and Chapter 8 describes the practical application of using (frus- trated) Lewis pairs to promote the polymerisation of a large range of monomer substrates.Chapter9thensummarises theutilisationoftransition metal complexes asone(or both) oftheLewisacidicorbasiccomponents inFLPs. Theveryrecent developments in radical formation and reactivity in FLP systems are discussed in Chapter10.Wearedelightedthatthefinalchaptertakesadifferenttackandrounds offallofthecutting-edgeresearchoftherestofthebook:Chapter11describesthe effectivenessoftheFLPframeworkasapedagogicaltoolforhelpingstudents(re-) learn fundamental thermodynamic concepts. WehopethatthisbookrunsthegamutofcatalysisbyfrustratedLewispairs,and will serve as both an inspiring read for those that are completely new to the field, and as a useful reference book for more experienced researchers. There is huge scopetoexpandontheworkdescribedinthesechaptersinthefuture,andthereare undoubtedly many discoveries that could spawn completely new chapters in upcoming books! We would once again like to thank all the authors of the chapters for their immense contributions to this book, and we hope you enjoy reading it. Birmingham, UK Andrew R. Jupp Amsterdam, The Netherlands J. Chris Slootweg July 2020 Contents 1 Frustrated Lewis Pair Catalysis: An Introduction . . . . . . . . . . . . . 1 Douglas W. Stephan 2 Frustrated Lewis Pair Catalyzed Asymmetric Reactions. . . . . . . . . 29 Xiangqing Feng, Wei Meng, and Haifeng Du 3 FLP Reduction of Carbon Monoxide and Related Reactions . . . . . 87 Tongdao Wang, Constantin G. Daniliuc, Gerald Kehr, and Gerhard Erker 4 FLP-Mediated C–H-Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 Yashar Soltani and Frédéric-Georges Fontaine 5 Mechanistic Insight into the Hydrogen Activation by Frustrated Lewis Pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 Mojgan Heshmat, Lei Liu, and Bernd Ensing 6 Lewis Acidic Boranes in Frustrated Lewis Pair Chemistry. . . . . . . 209 Theodore A. Gazis, Darren Willcox, and Rebecca L. Melen 7 Heterogeneous Catalysis by Frustrated Lewis Pairs . . . . . . . . . . . . 237 Andrew R. Jupp 8 Lewis Acid−Base Pairs for Polymerization Catalysis: Recent Progress and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . 283 Miao Hong 9 Frustrated Lewis Pairs Based on Transition Metals . . . . . . . . . . . . 319 Nereida Hidalgo, Macarena G. Alférez, and Jesús Campos 10 Radicals in Frustrated Lewis Pair Chemistry . . . . . . . . . . . . . . . . . 361 Flip Holtrop, Andrew R. Jupp, and J. Chris Slootweg vii viii Contents 11 Frustrated Lewis Pair Pedagogy: Expanding Core Undergraduate Curriculum and Reinforcing Fundamental Thermodynamic Concepts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387 Timothy C. Johnstone Index .... .... .... .... .... ..... .... .... .... .... .... ..... .... 401 Chapter 1 Frustrated Lewis Pair Catalysis: An Introduction DouglasW.Stephan Abstract ThischapterprovidesabriefoverviewoftheevolutionofFLPcatalysis. Webeginwithadescriptionoftheinitialfindingofreversiblehydrogenactivation andthedevelopmentofFLP-mediatedcatalytichydrogenations.Subsequently,the applicationsofFLPsinothercatalyticprocessesinvolvingothersmallmoleculesare considered.Theseincludehydrosilylation,transferhydrogenations,hydroboration, amination,hydroarylation,C–Hborylation,polymerization,CO reduction,andC–F 2 derivatization.Thechapterconcludeswithasummaryandshortdiscussionoffuture potential. · · · Keywords Frustratedlewispairs Hydrogenation Hydrosilylation Transfer · · · · · hydrogenations Hydroboration Amination Hydroarylation C–Hborylation · · Polymerization CO reduction C–Fderivatization 2 Abbreviations 9-BBN 9-Borabicyclo[3.3.1]nonane Ar Aryl atm Atmosphere bipy Bipyridine Bn Benzyl Bu Butyl cat Catechol Cat. Catalyst Cp Cyclopentadienide Cy Cyclohexyl DABCO 1,4-Diazabicyclo[2.2.2]octane EPC Electrophilicphosphoniumcation B D.W.Stephan( ) DepartmentofChemistry,UniversityofToronto,80St.GeorgeSt.,Toronto,ONM6S3H6,Canada e-mail:[email protected] ©SpringerNatureSwitzerlandAG2021 1 J.ChrisSlootwegandA.R.Jupp(eds.),FrustratedLewisPairs, MolecularCatalysis2,https://doi.org/10.1007/978-3-030-58888-5_1
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