Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements

Lucian Cristian Pop, Desmond Mac-Leod Carey, Alvaro Muñoz-Castro, Luminita Silaghi-Dumitrescu, Annie Castel, Ramiro Arratia-Pérez

Resultado de la investigación: Article

6 Citas (Scopus)

Resumen

The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin-orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes. Our results show an existence of a lack of systems 2-4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO's. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C5 ring is affected by the change of the pnictogen atom, while the aromaticity on the C7 ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.

Idioma originalEnglish
Páginas (desde-hasta)841-845
Número de páginas5
PublicaciónPolyhedron
Volumen30
N.º5
DOI
EstadoPublished - 24 mar 2011

Huella dactilar

Atoms
Chemical shift
chemical equilibrium
atoms
rings
Hamiltonians
Electrons
Charge density
Complexation
Electronic structure
Cations
Orbits
electrons
reactivity
Positive ions
Metals
Ligands
electronic structure
orbits
cations

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

Pop, Lucian Cristian ; Mac-Leod Carey, Desmond ; Muñoz-Castro, Alvaro ; Silaghi-Dumitrescu, Luminita ; Castel, Annie ; Arratia-Pérez, Ramiro. / Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements. En: Polyhedron. 2011 ; Vol. 30, N.º 5. pp. 841-845.
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abstract = "The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin-orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes. Our results show an existence of a lack of systems 2-4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO's. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C5 ring is affected by the change of the pnictogen atom, while the aromaticity on the C7 ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.",
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Pop, LC, Mac-Leod Carey, D, Muñoz-Castro, A, Silaghi-Dumitrescu, L, Castel, A & Arratia-Pérez, R 2011, 'Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements', Polyhedron, vol. 30, n.º 5, pp. 841-845. https://doi.org/10.1016/j.poly.2010.12.023

Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements. / Pop, Lucian Cristian; Mac-Leod Carey, Desmond; Muñoz-Castro, Alvaro; Silaghi-Dumitrescu, Luminita; Castel, Annie; Arratia-Pérez, Ramiro.

En: Polyhedron, Vol. 30, N.º 5, 24.03.2011, p. 841-845.

Resultado de la investigación: Article

TY - JOUR

T1 - Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements

AU - Pop, Lucian Cristian

AU - Mac-Leod Carey, Desmond

AU - Muñoz-Castro, Alvaro

AU - Silaghi-Dumitrescu, Luminita

AU - Castel, Annie

AU - Arratia-Pérez, Ramiro

PY - 2011/3/24

Y1 - 2011/3/24

N2 - The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin-orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes. Our results show an existence of a lack of systems 2-4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO's. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C5 ring is affected by the change of the pnictogen atom, while the aromaticity on the C7 ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.

AB - The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin-orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes. Our results show an existence of a lack of systems 2-4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO's. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C5 ring is affected by the change of the pnictogen atom, while the aromaticity on the C7 ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.

KW - Aminotroponiminate

KW - Aromaticity

KW - Pnictogen group

KW - Relativistic DFT

KW - Spin-orbit

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DO - 10.1016/j.poly.2010.12.023

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JO - Polyhedron

JF - Polyhedron

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