Diborylcarbenes as Reactive Intermediates in Double 1,2‐Rearrangements with Low Activation Enthalpies

Matthias Menzel; Heinz Jürgen Winkler; Tesfay Ablelom; Dirk Steiner; Stefan Fau; Gernot Frenking; Werner Massa; Armin Berndt

doi:10.1002/anie.199513401

Diborylcarbenes as Reactive Intermediates in Double 1,2‐Rearrangements with Low Activation Enthalpies

Matthias Menzel, Heinz Jürgen Winkler, Tesfay Ablelom, Dirk Steiner, Stefan Fau, Gernot Frenking, Werner Massa, Armin Berndt

University of Marburg

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

Despite three neighboring electron‐deficient centers, dicarborylcarbenes are not too high in energy to be accessible thermally. This was shown by the low activation enthalpies (≈22–23 kcal mol⁻¹) of double 1,2‐rearrangements of borylmethyleneboranes, in which alkyl groups migrate from carbon to boron and aryl groups from boron to carbon. Ab initio calculations reveal that tetramethyldiborylcarbene 2 is only 23.1 kcal mol⁻¹ higher in energy than tetramethylborylmethyleneborane 1. (Figure Presented.)

Original language	English
Pages (from-to)	1340-1343
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	34
Issue number	12
DOIs	https://doi.org/10.1002/anie.199513401
State	Published - 7 Jul 1995
Externally published	Yes

Keywords

ab initio calculations
boron compounds
carbenes
electron‐deficient compounds
rearrangements

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10.1002/anie.199513401

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title = "Diborylcarbenes as Reactive Intermediates in Double 1,2‐Rearrangements with Low Activation Enthalpies",

abstract = "Despite three neighboring electron‐deficient centers, dicarborylcarbenes are not too high in energy to be accessible thermally. This was shown by the low activation enthalpies (≈22–23 kcal mol−1) of double 1,2‐rearrangements of borylmethyleneboranes, in which alkyl groups migrate from carbon to boron and aryl groups from boron to carbon. Ab initio calculations reveal that tetramethyldiborylcarbene 2 is only 23.1 kcal mol−1 higher in energy than tetramethylborylmethyleneborane 1. (Figure Presented.)",

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T1 - Diborylcarbenes as Reactive Intermediates in Double 1,2‐Rearrangements with Low Activation Enthalpies

AU - Menzel, Matthias

AU - Winkler, Heinz Jürgen

AU - Ablelom, Tesfay

AU - Steiner, Dirk

AU - Fau, Stefan

AU - Frenking, Gernot

AU - Massa, Werner

AU - Berndt, Armin

PY - 1995/7/7

Y1 - 1995/7/7

N2 - Despite three neighboring electron‐deficient centers, dicarborylcarbenes are not too high in energy to be accessible thermally. This was shown by the low activation enthalpies (≈22–23 kcal mol−1) of double 1,2‐rearrangements of borylmethyleneboranes, in which alkyl groups migrate from carbon to boron and aryl groups from boron to carbon. Ab initio calculations reveal that tetramethyldiborylcarbene 2 is only 23.1 kcal mol−1 higher in energy than tetramethylborylmethyleneborane 1. (Figure Presented.)

AB - Despite three neighboring electron‐deficient centers, dicarborylcarbenes are not too high in energy to be accessible thermally. This was shown by the low activation enthalpies (≈22–23 kcal mol−1) of double 1,2‐rearrangements of borylmethyleneboranes, in which alkyl groups migrate from carbon to boron and aryl groups from boron to carbon. Ab initio calculations reveal that tetramethyldiborylcarbene 2 is only 23.1 kcal mol−1 higher in energy than tetramethylborylmethyleneborane 1. (Figure Presented.)

KW - ab initio calculations

KW - boron compounds

KW - carbenes

KW - electron‐deficient compounds

KW - rearrangements

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DO - 10.1002/anie.199513401

M3 - 文章

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SN - 1433-7851

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Diborylcarbenes as Reactive Intermediates in Double 1,2‐Rearrangements with Low Activation Enthalpies

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Keywords

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