Frustrated Lewis Pairs

408 Pages·2021·17.361 MB·English

by  J. Chris Slootweg, Andrew R. Jupp

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
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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
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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