The role of Cr, Mo and W in the electronic delocalization and the metal-ring interaction in metallocene complexes

David Arias-Olivares, Dayán Páez-Hernández, Rafael Islas

Resultado de la investigación: Article

1 Cita (Scopus)

Resumen

Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of Energy Decomposition Analysis (Morokuma-Ziegler), combined with Extended Transition State Natural Orbitals for Chemical Valence, finding that metal-ring bonding was a covalent contribution of about 60% due to the bonding interaction between dxz and dyz, dx2-y2 and dxy orbitals with pz orbitals, respectively, adapted by symmetry in the ring, to form π and δ bonding interactions. Finally, an important amount of electron density between the ring and the metal was found. This has a key role in the electron delocalization in this zone. This electronic delocalization was analysed via Induced Magnetic Field and Nucleus-Independent Chemical Shift calculations, finding a pattern between metal atomic radii and shielding tensor. Furthermore, similar behaviour for Mo and W, in the enhancement of the diatropic magnetic response, was displayed while Cr had a slightly lower diatropic character.

Idioma originalEnglish
Páginas (desde-hasta)5334-5344
Número de páginas11
PublicaciónNew Journal of Chemistry
Volumen42
N.º7
DOI
EstadoPublished - 1 ene 2018

Huella dactilar

Metals
Chemical shift
Benzene
Shielding
Tensors
Carrier concentration
Magnetic fields
Decomposition
metallocene
Electrons

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Citar esto

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abstract = "Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of Energy Decomposition Analysis (Morokuma-Ziegler), combined with Extended Transition State Natural Orbitals for Chemical Valence, finding that metal-ring bonding was a covalent contribution of about 60{\%} due to the bonding interaction between dxz and dyz, dx2-y2 and dxy orbitals with pz orbitals, respectively, adapted by symmetry in the ring, to form π and δ bonding interactions. Finally, an important amount of electron density between the ring and the metal was found. This has a key role in the electron delocalization in this zone. This electronic delocalization was analysed via Induced Magnetic Field and Nucleus-Independent Chemical Shift calculations, finding a pattern between metal atomic radii and shielding tensor. Furthermore, similar behaviour for Mo and W, in the enhancement of the diatropic magnetic response, was displayed while Cr had a slightly lower diatropic character.",
author = "David Arias-Olivares and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Rafael Islas",
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T1 - The role of Cr, Mo and W in the electronic delocalization and the metal-ring interaction in metallocene complexes

AU - Arias-Olivares, David

AU - Páez-Hernández, Dayán

AU - Islas, Rafael

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of Energy Decomposition Analysis (Morokuma-Ziegler), combined with Extended Transition State Natural Orbitals for Chemical Valence, finding that metal-ring bonding was a covalent contribution of about 60% due to the bonding interaction between dxz and dyz, dx2-y2 and dxy orbitals with pz orbitals, respectively, adapted by symmetry in the ring, to form π and δ bonding interactions. Finally, an important amount of electron density between the ring and the metal was found. This has a key role in the electron delocalization in this zone. This electronic delocalization was analysed via Induced Magnetic Field and Nucleus-Independent Chemical Shift calculations, finding a pattern between metal atomic radii and shielding tensor. Furthermore, similar behaviour for Mo and W, in the enhancement of the diatropic magnetic response, was displayed while Cr had a slightly lower diatropic character.

AB - Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of Energy Decomposition Analysis (Morokuma-Ziegler), combined with Extended Transition State Natural Orbitals for Chemical Valence, finding that metal-ring bonding was a covalent contribution of about 60% due to the bonding interaction between dxz and dyz, dx2-y2 and dxy orbitals with pz orbitals, respectively, adapted by symmetry in the ring, to form π and δ bonding interactions. Finally, an important amount of electron density between the ring and the metal was found. This has a key role in the electron delocalization in this zone. This electronic delocalization was analysed via Induced Magnetic Field and Nucleus-Independent Chemical Shift calculations, finding a pattern between metal atomic radii and shielding tensor. Furthermore, similar behaviour for Mo and W, in the enhancement of the diatropic magnetic response, was displayed while Cr had a slightly lower diatropic character.

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