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N-Heterocyclic Carbenes in FLP Chemistry

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Frustrated Lewis Pairs II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 334))

Abstract

The use of N-heterocyclic carbenes (NHCs) for the design and construction of frustrated Lewis pairs (FLPs) is outlined in this review. Stable carbene–borane adducts are briefly discussed, followed by a detailed survey of the reactivity of NHCs, in particular Arduengo-type imidazolin-2-ylidenes, towards B(C6F5)3. Structural and electronic NHC modification by variation of substituents and ring-size affords either stable normal adducts or FLPs, which undergo manifold deactivation reactions in the absence of substrates, e.g., by abnormal adduct formation, self-dehydrogenation, and other types of C–H and C–F bond activation. The degree of frustration is correlated with the calculated energies for the formation of the normal adducts NHC·B(C6F5)3, allowing one to predict and rationalize their reactivity towards small molecules such as dihydrogen, ethers, alkynes, main group elements, carbon dioxide, and nitrous oxide. Other carbene-based FLP systems with a variety of alternative Lewis acids such as boranes, alanes, and carbon-based Lewis acids are also covered, whenever “frustration” is observed. A brief introduction of structurally related bifunctional FLPs based on borylated N-heterocycles is also included.

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Abbreviations

9-BBN:

9-Borabicyclo [3.3.1]nonane

Alk:

Alkyl

Ar:

Aryl

Bu:

Butyl

d:

Day(s)

Dipp:

1,3-Diisopropylphenyl

equiv.:

Equivalent(s)

Et:

Ethyl

FLP:

Frustrated Lewis pair

h:

Hour(s)

Hal:

Halogen

iPr:

Isopropyl

Me:

Methyl

Mes:

Mesityl, 2,4,6-trimethylphenyl (not methanesulfonyl)

min:

Minute(s)

mol:

Mole(s)

NHC:

N-Heterocyclic carbene

Nu:

Nucleophile

Ph:

Phenyl

Pr:

Propyl

rt:

Room temperature

tBu:

tert-butyl

THF:

Tetrahydrofuran

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  1. Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany

    Eugene L. Kolychev, Eileen Theuergarten & Matthias Tamm

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  1. Eugene L. Kolychev
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  2. Eileen Theuergarten
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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, Ontario, Canada

    Douglas W. Stephan

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Kolychev, E.L., Theuergarten, E., Tamm, M. (2012). N-Heterocyclic Carbenes in FLP Chemistry. In: Erker, G., Stephan, D. (eds) Frustrated Lewis Pairs II. Topics in Current Chemistry, vol 334. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2012_379

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