[2.2.2]Paracyclophane, preference for η6 or η18 coordination mode including Ag(I) and Sn(II): A survey into the cation-π interaction nature through relativistic DFT calculations

Carolina Olea Ulloa, Miguel Ponce-Vargas, Rafael De Mattos Piccoli, Giovanni F. Caramori, Gernot Frenking, Alvaro Muñoz-Castro

Resultado de la investigación: Article

19 Citas (Scopus)

Resumen

[2.2.2]Paracyclophane is a versatile π-cryptating structure, which can exhibit η222 and η666 coordination with metal ions, involving two or six carbon atoms in each aromatic ring. According to the nature of the metallic cation, the interaction can occur at the centre of the cage or upper face of the structure, which is determined mainly by the ligand-to-metal charge transfer ruled by symmetry and energetic considerations, and thus by the nature of the cation-π interaction. For Ag(I), the 5s-Ag shell is close in energy to the frontier orbitals of paracyclophane, resulting in the formation of a bonding combination with the symmetric combination of the π2-type levels, which leads to a non-centered conformation. In contrast, the Sn(II) case exhibits a largely favourable bonding interaction with the π2 and π3 type levels, which involve the 5p-Sn shell and result in a centered conformation. The interaction between the metal and paracyclophane was studied via molecular orbitals diagram, energy decomposition analyses (EDA) and non-covalent indexes (NCI).

Idioma originalEnglish
Páginas (desde-hasta)7803-7811
Número de páginas9
PublicaciónRSC Advances
Volumen5
N.º11
DOI
EstadoPublished - 2015
Publicado de forma externa

Huella dactilar

Discrete Fourier transforms
Conformations
Cations
Positive ions
Metals
Molecular orbitals
Metal ions
Charge transfer
Carbon
Ligands
Decomposition
Atoms

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Citar esto

Ulloa, Carolina Olea ; Ponce-Vargas, Miguel ; De Mattos Piccoli, Rafael ; Caramori, Giovanni F. ; Frenking, Gernot ; Muñoz-Castro, Alvaro. / [2.2.2]Paracyclophane, preference for η6 or η18 coordination mode including Ag(I) and Sn(II) : A survey into the cation-π interaction nature through relativistic DFT calculations. En: RSC Advances. 2015 ; Vol. 5, N.º 11. pp. 7803-7811.
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title = "[2.2.2]Paracyclophane, preference for η6 or η18 coordination mode including Ag(I) and Sn(II): A survey into the cation-π interaction nature through relativistic DFT calculations",
abstract = "[2.2.2]Paracyclophane is a versatile π-cryptating structure, which can exhibit η2:η2:η2 and η6:η6:η6 coordination with metal ions, involving two or six carbon atoms in each aromatic ring. According to the nature of the metallic cation, the interaction can occur at the centre of the cage or upper face of the structure, which is determined mainly by the ligand-to-metal charge transfer ruled by symmetry and energetic considerations, and thus by the nature of the cation-π interaction. For Ag(I), the 5s-Ag shell is close in energy to the frontier orbitals of paracyclophane, resulting in the formation of a bonding combination with the symmetric combination of the π2-type levels, which leads to a non-centered conformation. In contrast, the Sn(II) case exhibits a largely favourable bonding interaction with the π2 and π3 type levels, which involve the 5p-Sn shell and result in a centered conformation. The interaction between the metal and paracyclophane was studied via molecular orbitals diagram, energy decomposition analyses (EDA) and non-covalent indexes (NCI).",
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[2.2.2]Paracyclophane, preference for η6 or η18 coordination mode including Ag(I) and Sn(II) : A survey into the cation-π interaction nature through relativistic DFT calculations. / Ulloa, Carolina Olea; Ponce-Vargas, Miguel; De Mattos Piccoli, Rafael; Caramori, Giovanni F.; Frenking, Gernot; Muñoz-Castro, Alvaro.

En: RSC Advances, Vol. 5, N.º 11, 2015, p. 7803-7811.

Resultado de la investigación: Article

TY - JOUR

T1 - [2.2.2]Paracyclophane, preference for η6 or η18 coordination mode including Ag(I) and Sn(II)

T2 - A survey into the cation-π interaction nature through relativistic DFT calculations

AU - Ulloa, Carolina Olea

AU - Ponce-Vargas, Miguel

AU - De Mattos Piccoli, Rafael

AU - Caramori, Giovanni F.

AU - Frenking, Gernot

AU - Muñoz-Castro, Alvaro

PY - 2015

Y1 - 2015

N2 - [2.2.2]Paracyclophane is a versatile π-cryptating structure, which can exhibit η2:η2:η2 and η6:η6:η6 coordination with metal ions, involving two or six carbon atoms in each aromatic ring. According to the nature of the metallic cation, the interaction can occur at the centre of the cage or upper face of the structure, which is determined mainly by the ligand-to-metal charge transfer ruled by symmetry and energetic considerations, and thus by the nature of the cation-π interaction. For Ag(I), the 5s-Ag shell is close in energy to the frontier orbitals of paracyclophane, resulting in the formation of a bonding combination with the symmetric combination of the π2-type levels, which leads to a non-centered conformation. In contrast, the Sn(II) case exhibits a largely favourable bonding interaction with the π2 and π3 type levels, which involve the 5p-Sn shell and result in a centered conformation. The interaction between the metal and paracyclophane was studied via molecular orbitals diagram, energy decomposition analyses (EDA) and non-covalent indexes (NCI).

AB - [2.2.2]Paracyclophane is a versatile π-cryptating structure, which can exhibit η2:η2:η2 and η6:η6:η6 coordination with metal ions, involving two or six carbon atoms in each aromatic ring. According to the nature of the metallic cation, the interaction can occur at the centre of the cage or upper face of the structure, which is determined mainly by the ligand-to-metal charge transfer ruled by symmetry and energetic considerations, and thus by the nature of the cation-π interaction. For Ag(I), the 5s-Ag shell is close in energy to the frontier orbitals of paracyclophane, resulting in the formation of a bonding combination with the symmetric combination of the π2-type levels, which leads to a non-centered conformation. In contrast, the Sn(II) case exhibits a largely favourable bonding interaction with the π2 and π3 type levels, which involve the 5p-Sn shell and result in a centered conformation. The interaction between the metal and paracyclophane was studied via molecular orbitals diagram, energy decomposition analyses (EDA) and non-covalent indexes (NCI).

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