Global and local reactivity of N-heterocyclic carbenes with boron and phosphorus atoms: An analysis based on spin polarized density functional framework

Resultado de la investigación: Article

5 Citas (Scopus)

Resumen

A global and local analysis on some N-heterocyclic carbenes containing boron and phosphorus atoms has been performed within the spin polarized density functional theory (SP-DFT) framework. The philicities for spin polarization have been found linearly related to the triplet-singlet energy gap along this series. In agreement with the experimental evidence, these compounds exhibit very low values of the electrophilicity index. In order to gain further insights into the bonding nature and charge and spin reorganization to spin polarization processes associated to these compounds; local considerations were made using simple model approximations to SP-DFT Fukui descriptors. A higher depletion of density of charge is observed in the boron and phosphorus carbenes as compared with imidazol-2-ylidene taken as the reference compound, whereas the spin density is shown to be accumulated on the carbenic carbon atom in all compounds. The SP-DFT indices used here allow us to assess that the aluminum analogue compounds have a slightly higher electrophilic character than the boron compounds, in agreement with previous experimental results.

Idioma originalEnglish
Páginas (desde-hasta)110-114
Número de páginas5
PublicaciónJournal of Molecular Structure: THEOCHEM
Volumen943
N.º1-3
DOI
EstadoPublished - 15 mar 2010

Huella dactilar

Boron
carbenes
Phosphorus
Density functional theory
phosphorus
Spin polarization
boron
Aluminum Compounds
reactivity
Boron Compounds
Atoms
atoms
Carbon
Aluminum
density functional theory
Energy gap
boron compounds
polarization
carbene
imidazoles

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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title = "Global and local reactivity of N-heterocyclic carbenes with boron and phosphorus atoms: An analysis based on spin polarized density functional framework",
abstract = "A global and local analysis on some N-heterocyclic carbenes containing boron and phosphorus atoms has been performed within the spin polarized density functional theory (SP-DFT) framework. The philicities for spin polarization have been found linearly related to the triplet-singlet energy gap along this series. In agreement with the experimental evidence, these compounds exhibit very low values of the electrophilicity index. In order to gain further insights into the bonding nature and charge and spin reorganization to spin polarization processes associated to these compounds; local considerations were made using simple model approximations to SP-DFT Fukui descriptors. A higher depletion of density of charge is observed in the boron and phosphorus carbenes as compared with imidazol-2-ylidene taken as the reference compound, whereas the spin density is shown to be accumulated on the carbenic carbon atom in all compounds. The SP-DFT indices used here allow us to assess that the aluminum analogue compounds have a slightly higher electrophilic character than the boron compounds, in agreement with previous experimental results.",
keywords = "Charge transfer, N-Heterocyclic carbenes, Philicity, Spin polarization, Spin polarized density functional theory",
author = "Patricia P{\'e}rez and Eduardo Chamorro",
year = "2010",
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language = "English",
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TY - JOUR

T1 - Global and local reactivity of N-heterocyclic carbenes with boron and phosphorus atoms

T2 - An analysis based on spin polarized density functional framework

AU - Pérez, Patricia

AU - Chamorro, Eduardo

PY - 2010/3/15

Y1 - 2010/3/15

N2 - A global and local analysis on some N-heterocyclic carbenes containing boron and phosphorus atoms has been performed within the spin polarized density functional theory (SP-DFT) framework. The philicities for spin polarization have been found linearly related to the triplet-singlet energy gap along this series. In agreement with the experimental evidence, these compounds exhibit very low values of the electrophilicity index. In order to gain further insights into the bonding nature and charge and spin reorganization to spin polarization processes associated to these compounds; local considerations were made using simple model approximations to SP-DFT Fukui descriptors. A higher depletion of density of charge is observed in the boron and phosphorus carbenes as compared with imidazol-2-ylidene taken as the reference compound, whereas the spin density is shown to be accumulated on the carbenic carbon atom in all compounds. The SP-DFT indices used here allow us to assess that the aluminum analogue compounds have a slightly higher electrophilic character than the boron compounds, in agreement with previous experimental results.

AB - A global and local analysis on some N-heterocyclic carbenes containing boron and phosphorus atoms has been performed within the spin polarized density functional theory (SP-DFT) framework. The philicities for spin polarization have been found linearly related to the triplet-singlet energy gap along this series. In agreement with the experimental evidence, these compounds exhibit very low values of the electrophilicity index. In order to gain further insights into the bonding nature and charge and spin reorganization to spin polarization processes associated to these compounds; local considerations were made using simple model approximations to SP-DFT Fukui descriptors. A higher depletion of density of charge is observed in the boron and phosphorus carbenes as compared with imidazol-2-ylidene taken as the reference compound, whereas the spin density is shown to be accumulated on the carbenic carbon atom in all compounds. The SP-DFT indices used here allow us to assess that the aluminum analogue compounds have a slightly higher electrophilic character than the boron compounds, in agreement with previous experimental results.

KW - Charge transfer

KW - N-Heterocyclic carbenes

KW - Philicity

KW - Spin polarization

KW - Spin polarized density functional theory

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U2 - 10.1016/j.theochem.2009.11.011

DO - 10.1016/j.theochem.2009.11.011

M3 - Article

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VL - 943

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EP - 114

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

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