Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re2(CO) 8(μ-BiPh)2] and [Re2(CO)8(μ- BiPh2)2] clusters

Eduardo Schott; Ximena Zárate; Ramiro Arratia-Pérez

doi:10.1016/j.poly.2010.12.022

Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re₂(CO) ₈(μ-BiPh)₂] and [Re₂(CO)₈(μ- BiPh₂)₂] clusters

Eduardo Schott
, Ximena Zárate
, Ramiro Arratia-Pérez

Exact Sciences School

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re₂(CO)₈(μ-BiPh)₂] and [Re₂(CO)₈(μ-BiPh₂)₂] clusters are reported. We show here that the [Re₂(CO)₈(μ-BiPh) ₂] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re₂(CO)₈(μ-BiPh₂)₂] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.

Original language	English
Pages (from-to)	846-850
Number of pages	5
Journal	Polyhedron
Volume	30
Issue number	5
DOIs	https://doi.org/10.1016/j.poly.2010.12.022
Publication status	Published - 24 Mar 2011

Keywords

Bismuth
ELF
NICS
Relativistic DFT
Rhenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.poly.2010.12.022

Cite this

@article{2845b3eeb28b4c3b8768e71e4d9b7d60,

title = "Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re2(CO) 8(μ-BiPh)2] and [Re2(CO)8(μ- BiPh2)2] clusters",

abstract = "Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters are reported. We show here that the [Re2(CO)8(μ-BiPh) 2] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re2(CO)8(μ-BiPh2)2] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.",

keywords = "Bismuth, ELF, NICS, Relativistic DFT, Rhenium",

author = "Eduardo Schott and Ximena Z{\'a}rate and Ramiro Arratia-P{\'e}rez",

year = "2011",

month = mar,

day = "24",

doi = "10.1016/j.poly.2010.12.022",

language = "English",

volume = "30",

pages = "846--850",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

number = "5",

}

Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re₂(CO) ₈(μ-BiPh)₂] and [Re₂(CO)₈(μ- BiPh₂)₂] clusters. / Schott, Eduardo; Zárate, Ximena; Arratia-Pérez, Ramiro.
In: Polyhedron, Vol. 30, No. 5, 24.03.2011, p. 846-850.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Relativistic scalar and spin-orbit density functional calculations of the electronic structure, NICS index and ELF function of the [Re2(CO) 8(μ-BiPh)2] and [Re2(CO)8(μ- BiPh2)2] clusters

AU - Schott, Eduardo

AU - Zárate, Ximena

AU - Arratia-Pérez, Ramiro

PY - 2011/3/24

Y1 - 2011/3/24

N2 - Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters are reported. We show here that the [Re2(CO)8(μ-BiPh) 2] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re2(CO)8(μ-BiPh2)2] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.

AB - Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters are reported. We show here that the [Re2(CO)8(μ-BiPh) 2] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re2(CO)8(μ-BiPh2)2] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character.

KW - Bismuth

KW - ELF

KW - NICS

KW - Relativistic DFT

KW - Rhenium

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DO - 10.1016/j.poly.2010.12.022

M3 - Article

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