Understanding the chemical reactivity of phenylhalocarbene systems: an analysis based on the spin-polarized density functional theory

Guerra, Doris; Andrés, Juán; Chamorro, Eduardo; Pérez, Patricia

doi:10.1007/s00214-007-0263-0

Cited by 17 publications

(6 citation statements)

References 98 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As already mentioned in Section , the uniqueness of carbenes results from their specific electronic structure, which in turn can be explained by adequate electron occupancies of the carbene carbon's orbitals (Figure ). In turn, their reactivity and formation of various complexes are often discussed in the light of their nucleophilic or electrophilic properties . It is understood that carbenes, which through the interaction between the empty orbital p and the hydridic hydrogen atom of a silane should be prone to form the hydride‐carbene bond, should rather be characterized by considerable electrophilicity.…”

Section: Resultsmentioning

confidence: 99%

“…Based on these entities, Parr et al proposed the so‐called electrophilicity index

ω = \frac{μ^{2}}{2 η}

as a measure of electrophilicity of an atom or a molecule . This index was then readily used to describe electrophilic properties of various atoms and molecules, including carbenes . By utilizing finite difference approximation, one obtains μ = −1/2( I + A ) and η = I − A , hence

ω = \frac{{false(I + A false)}^{2}}{8 false(I - A false)},

where I and A are ionization potential and electron affinity, respectively.…”

Section: Carbene Electrophilicitymentioning

confidence: 99%

“…By utilizing finite difference approximation, one obtains μ = −1/2( I + A ) and η = I − A , hence

ω = \frac{{false(I + A false)}^{2}}{8 false(I - A false)},

where I and A are ionization potential and electron affinity, respectively. Quite often, energies of HOMO and LUMO are used for I and A , respectively, but it must be remembered that Koompans' theorem, according to which I 1 = − ε HOMO , applies only to the Hartree‐Fock method . Moreover, although generalization of Koompans' theorem to the electron affinity gives A = − ε L UMO , the use of this formula is untrustworthy because virtual orbitals are only by‐product of one‐electron approximation.…”

Section: Carbene Electrophilicitymentioning

confidence: 99%

See 2 more Smart Citations

In search for a hydride‐carbene bond

Jabłoński

2019

J of Physical Organic Chem

View full text Add to dashboard Cite

By presenting a large group of dimers featuring hydride-carbene bond between silane and various carbenes, we show that electrophilic properties of singlet carbenes can manifest also to a hydridic, ie, negatively charged, hydrogen atom of a hydride. This type of interaction is traced by the corresponding bond path in 18 cases. However, taking into account the fact that in the case of large interatomic distances, the electrostatic potential maps are better indicators of dominant intermolecular interactions, it is shown that the amount of dimers with the hydride-carbene bond is even larger, as indicated by both the proximity and correct orientation of the -hole on the carbene carbon atom and the negative surface of the hydridic hydrogen of the silane molecule. The hydride-carbene bond is weak, especially when compared with the hydride-triel bond also involving the silane. In contrast to the latter, the intermolecular charge transfer is negligible. Moreover, the local electrostatic interaction involving the carbene carbon's -hole is not necessarily predominant in stabilization of all the carbene· · ·silane complexes.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Based on these entities, Parr et al proposed the so‐called electrophilicity index

ω = \frac{μ^{2}}{2 η}

ω = \frac{{false(I + A false)}^{2}}{8 false(I - A false)},

where I and A are ionization potential and electron affinity, respectively.…”

Section: Carbene Electrophilicitymentioning

confidence: 99%

“…By utilizing finite difference approximation, one obtains μ = −1/2( I + A ) and η = I − A , hence

ω = \frac{{false(I + A false)}^{2}}{8 false(I - A false)},

Section: Carbene Electrophilicitymentioning

confidence: 99%

See 1 more Smart Citation

In search for a hydride‐carbene bond

Jabłoński

2019

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…39 The results indicated that the addition of phenylhalocarbenes to alkenes is a single-step reaction controlled by the carbene electrophilicity.…”

Section: Generation Structure and Reactivitymentioning

confidence: 98%

Carbenes and Nitrenes

Gras

2007

Organic Reaction Mechanisms Series

View full text Add to dashboard Cite

“…Chattaraj et al have stressed the usefulness of a generalized local index of philicity [62], which is aimed to be successful to describe electrophilic, nucleophilic, and radical reactions [64,65]. Extensions of such kind of descriptors into the framework of spin-polarized version of DFT have been also recently explored [66][67][68][69][70][71][72]. The local philicity has indeed demonstrated to be another useful tool to describe chemical reactivity and selectivity in several practical problems [73].…”

Section: Introductionmentioning

confidence: 99%