Monoheteroatom substituted six-membered carbenes: A computational survey of stability and reactivity

M. R. Momeni; F. A. Shakib

doi:10.1016/j.comptc.2011.01.033

Monoheteroatom substituted six-membered carbenes: A computational survey of stability and reactivity

M. R. Momeni, F. A. Shakib

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2 Scopus citations

Abstract

1-(X)-3,3-dimethyl-2-cyclohexanylidenes, where X = amino, oxy, phosphino, and thio, are compared and contrasted to probe the effect of monoheteroatom substitution on the stability, multiplicity and reactivity of six-membered saturated and unsaturated cyclic carbenes. The stabilizing effects of substituents are discussed through geometrical parameters, and AIM analysis. The strong π-donor/σ-acceptor amino group exerts singlet-triplet energy separation (ΔE_S-T) of 38.4 kcal/mol while more electronegative oxy group induces a ΔE_S-T of 23.0 kcal/mol. Aminoalkylcarbenes rebuff dimerization while oxyalkylcarbenes show a high dimerizing affinity. The reactivity of species is discussed in terms of nucleophilicity and electrophilicity indices as well as proton affinities. It seems that our six-membered carbenes are more nucleophilic than common five-membered N-heterocyclic carbenes.

Original language	English (US)
Pages (from-to)	101-106
Number of pages	6
Journal	Computational and Theoretical Chemistry
Volume	965
Issue number	1
DOIs	https://doi.org/10.1016/j.comptc.2011.01.033
State	Published - Apr 2011
Externally published	Yes

All Science Journal Classification (ASJC) codes

Biochemistry
Condensed Matter Physics
Physical and Theoretical Chemistry

Keywords

Aminoalkylcarbene
DFT
Nucleophilicity
Phosphinoalkylcarbene
Stability

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10.1016/j.comptc.2011.01.033

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title = "Monoheteroatom substituted six-membered carbenes: A computational survey of stability and reactivity",

abstract = "1-(X)-3,3-dimethyl-2-cyclohexanylidenes, where X = amino, oxy, phosphino, and thio, are compared and contrasted to probe the effect of monoheteroatom substitution on the stability, multiplicity and reactivity of six-membered saturated and unsaturated cyclic carbenes. The stabilizing effects of substituents are discussed through geometrical parameters, and AIM analysis. The strong π-donor/σ-acceptor amino group exerts singlet-triplet energy separation (ΔES-T) of 38.4 kcal/mol while more electronegative oxy group induces a ΔES-T of 23.0 kcal/mol. Aminoalkylcarbenes rebuff dimerization while oxyalkylcarbenes show a high dimerizing affinity. The reactivity of species is discussed in terms of nucleophilicity and electrophilicity indices as well as proton affinities. It seems that our six-membered carbenes are more nucleophilic than common five-membered N-heterocyclic carbenes.",

keywords = "Aminoalkylcarbene, DFT, Nucleophilicity, Phosphinoalkylcarbene, Stability",

author = "Momeni, {M. R.} and Shakib, {F. A.}",

year = "2011",

month = apr,

doi = "10.1016/j.comptc.2011.01.033",

language = "English (US)",

volume = "965",

pages = "101--106",

journal = "Computational and Theoretical Chemistry",

issn = "2210-271X",

publisher = "Elsevier BV",

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T1 - Monoheteroatom substituted six-membered carbenes

T2 - A computational survey of stability and reactivity

AU - Momeni, M. R.

AU - Shakib, F. A.

PY - 2011/4

Y1 - 2011/4

N2 - 1-(X)-3,3-dimethyl-2-cyclohexanylidenes, where X = amino, oxy, phosphino, and thio, are compared and contrasted to probe the effect of monoheteroatom substitution on the stability, multiplicity and reactivity of six-membered saturated and unsaturated cyclic carbenes. The stabilizing effects of substituents are discussed through geometrical parameters, and AIM analysis. The strong π-donor/σ-acceptor amino group exerts singlet-triplet energy separation (ΔES-T) of 38.4 kcal/mol while more electronegative oxy group induces a ΔES-T of 23.0 kcal/mol. Aminoalkylcarbenes rebuff dimerization while oxyalkylcarbenes show a high dimerizing affinity. The reactivity of species is discussed in terms of nucleophilicity and electrophilicity indices as well as proton affinities. It seems that our six-membered carbenes are more nucleophilic than common five-membered N-heterocyclic carbenes.

AB - 1-(X)-3,3-dimethyl-2-cyclohexanylidenes, where X = amino, oxy, phosphino, and thio, are compared and contrasted to probe the effect of monoheteroatom substitution on the stability, multiplicity and reactivity of six-membered saturated and unsaturated cyclic carbenes. The stabilizing effects of substituents are discussed through geometrical parameters, and AIM analysis. The strong π-donor/σ-acceptor amino group exerts singlet-triplet energy separation (ΔES-T) of 38.4 kcal/mol while more electronegative oxy group induces a ΔES-T of 23.0 kcal/mol. Aminoalkylcarbenes rebuff dimerization while oxyalkylcarbenes show a high dimerizing affinity. The reactivity of species is discussed in terms of nucleophilicity and electrophilicity indices as well as proton affinities. It seems that our six-membered carbenes are more nucleophilic than common five-membered N-heterocyclic carbenes.

KW - Aminoalkylcarbene

KW - DFT

KW - Nucleophilicity

KW - Phosphinoalkylcarbene

KW - Stability

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JO - Computational and Theoretical Chemistry

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ER -

Monoheteroatom substituted six-membered carbenes: A computational survey of stability and reactivity

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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