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Frustrated Lewis Pairs I pp 45–83Cite as

Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 332))

Abstract

Intramolecular vicinal and geminal frustrated Lewis pairs (FLPs) featuring bulky substituents at phosphorus or nitrogen and strongly electron-withdrawing bulky pentafluorophenyl substituents at boron undergo a variety of addition and/or activation reactions with small molecules. A number of examples of such reactions are presented and discussed, among them the FLP activation of dihydrogen to give zwitterionic phosphonium (or ammonium)/hydridoborate zwitterions. Intramolecular FLPs also add to organic carbonyl compounds (including carbon dioxide), to alkenes and alkynes (including conjugated dienes, diynes or enynes), to heterocumulenes, to azides, and to nitric oxide.

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Abbreviations

Bu:

Butyl

CP:

Cross polarization

DABCO:

1,4-Diazabicyclo[2.2.2]octane

DEAD:

Diethyl azodicarboxylate

DFT:

Density functional theory

equiv.:

Equivalent(s)

Et:

Ethyl

FLP:

Frustrated Lewis pair

gem.:

Geminal

h:

Hour(s)

HAA:

Hydrogen atom abstraction

i-Pr:

iso-Propyl

LA:

Lewis acid

LB:

Lewis base

MAS:

Magic angle spinning

Me:

Methyl

Mes:

Mesityl, 2,4,6-trimethylphenyl

min:

Minute(s)

NMR:

Nuclear magnetic resonance

Ph:

Phenyl

Pr:

Propyl

r.t.:

Room temperature

s-Bu:

sec-Butyl

THF:

Tetrahydrofuran

t-Bu:

tert-Butyl

vic.:

Vicinal

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Acknowledgment

G. E. thanks his co-workers at Münster for their great contributions to this exciting field. We cordially thank the collaborating groups. For all of us it has been a pleasure to work together and discover new FLP reactions and FLP behavior. G. E. thanks the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, the Alexander von Humboldt-Stiftung, and the European Research Council for financial support.

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  1. Organisch-Chemisches Institut der Universität Münster, Corrensstr. 40, 48149, Münster, Germany

    Gerald Kehr, Sina Schwendemann & Gerhard Erker

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  1. Gerald Kehr
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  2. Sina Schwendemann
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  3. Gerhard Erker
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Correspondence to Gerhard Erker .

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  1. Organisch-Chemisches Institut, Universität Münster, Corrensstr. 40, Münster, 48149, Germany

    Gerhard Erker

  2. Department of Chemistry, University of Toronto, St. George Street 80, Toronto, M5S 3H6, Canada

    Douglas W. Stephan

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Kehr, G., Schwendemann, S., Erker, G. (2012). Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features. In: Erker, G., Stephan, D. (eds) Frustrated Lewis Pairs I. Topics in Current Chemistry, vol 332. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2012_373

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