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Frustrated Lewis Pairs I pp 267–289Cite as

Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs

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

Abstract

Computational studies that characterize the effects of Lewis acidity/basicity on FLP formation and reactivity are reviewed. Formation of the FLP encounter complex “cage” depends on Lewis acidities and basicities of substituent “external” atoms, and their abilities to interact intramolecularly. Computations indicate that these interactions are worth 9–18 kcal mol−1 for partly fluorinated FLPs such as (F5C6)3B···P(t-Bu)3, and less for less fluorinated species such as (H5C6)3B···P(t-Bu)3. Reactivity within the cage depends on the “classical” Lewis acidities/basicities of the internal atoms. Energetics here fall into the range of 5–50 kcal mol−1; the larger the value, the greater the ability of the FLP to capture or split a substrate. In several cases the computationally predicted reaction barriers differ little with internal Lewis acidity/basicity, indicating that the rate-determining step involves the substrate entering the cage rather than attack by the Lewis acid/base atoms. In others, barriers vary sizably with Lewis acidity/basicity, indicating the opposite. In one case it was shown that these effects cancel, such that the three component barriers are identical for a range of substituted Lewis acid FLP components.

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Abbreviations

ABCO:

Azabicyclo[2,2,2]octane

Ad:

1-Adamantyl

Ar:

Arene or aryl

DABCO:

Diazabicyclo[2,2,2]octane

DFT:

Density functional theory

Dipp:

2,6-Di-(i-propyl)phenyl

FLP:

Frustrated Lewis pair

LA:

Lewis acid

LB:

Lewis base

Mes:

1,3,5-C6Me3H2

NHC:

N-Heterocyclic carbene

OG2R3:

3-Layer ONIOM-based G2R composite theory

ONI:

ONIOM-based composite method

Py:

Pyridine

SCRF:

Self consistent reaction field; continuum solvent correction model

Tmp:

2,2,6,6-Tetramethylpiperidine

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Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA

    Thomas M. Gilbert

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  1. Thomas M. Gilbert
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Correspondence to Thomas M. Gilbert .

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Editors and Affiliations

  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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Gilbert, T.M. (2012). Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs. 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_378

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