Electronic structure and molecular properties of binuclear group VII pentalene metal carbonyl complexes [C8H6{M(CO3)}2] (M = Mn, Tc, Re, Bh): A relativistic density functional theory study

A. Muñoz-Castro, D. Mac-Leod Carey, R. Arratia-Pérez

Resultado de la investigación: Article

10 Citas (Scopus)

Resumen

Homobimetallic systems where the metals are linked through a pentalenediide ligand, of the type anti-[Pn{M(CO)3}2] (Pn = pentalenediide), which include transition metals of the group VII with M = 25Mn (1), 43Tc (2), 73Re (3) and 107Bh (4), and the syn-[Pn{M(CO)3}2] isomer with M = 25Mn (s1), 43Tc (s2), 73Re (s3) and 107Bh (s4), were studied with relativistic all-electron density functional (DFT) calculations, including spin-orbit (SO) coupling via the two components ZORA Hamiltonian. The electronic structure was studied in detail in the four systems. Broken symmetry calculations were performed for all the paramagnetic systems to verify their mixed-valence character. The infrared (IR) spectra were obtained at the scalar relativistic regime and the UV-Vis was obtained by time-dependent spin-orbit DFT and compared against the experimental data available (only for 1 and 3). The relative binding energy calculations predict that the not yet reported s1, 2, s2, 4 and s4 complexes may be synthesized. Their optical and vibrational properties are described here. Due to the relativistic indirect effect acting on metal d orbitals there is an increased overlap between the nd and 2π* empty carbonyl orbitals, and hence the backbonding effect increases from 1/s1 to 4/s4. The calculated spin-dependent properties of the anionic complexes reveals that the isotropic g tensor decreases down the group, showing that the quenching of the total angular momentum of the unpaired electron increases along the group.

Idioma originalEnglish
Páginas (desde-hasta)1561-1567
Número de páginas7
PublicaciónPolyhedron
Volumen28
N.º8
DOI
EstadoPublished - 10 jun 2009

Huella dactilar

molecular properties
Carbon Monoxide
Electronic structure
Density functional theory
Orbits
Metals
density functional theory
electronic structure
Hamiltonians
Angular momentum
Binding energy
Isomers
metals
Transition metals
Tensors
Carrier concentration
orbits
Quenching
orbitals
Ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

@article{0dcc6cf276d940edbecfdf991cdabbd2,
title = "Electronic structure and molecular properties of binuclear group VII pentalene metal carbonyl complexes [C8H6{M(CO3)}2] (M = Mn, Tc, Re, Bh): A relativistic density functional theory study",
abstract = "Homobimetallic systems where the metals are linked through a pentalenediide ligand, of the type anti-[Pn{M(CO)3}2] (Pn = pentalenediide), which include transition metals of the group VII with M = 25Mn (1), 43Tc (2), 73Re (3) and 107Bh (4), and the syn-[Pn{M(CO)3}2] isomer with M = 25Mn (s1), 43Tc (s2), 73Re (s3) and 107Bh (s4), were studied with relativistic all-electron density functional (DFT) calculations, including spin-orbit (SO) coupling via the two components ZORA Hamiltonian. The electronic structure was studied in detail in the four systems. Broken symmetry calculations were performed for all the paramagnetic systems to verify their mixed-valence character. The infrared (IR) spectra were obtained at the scalar relativistic regime and the UV-Vis was obtained by time-dependent spin-orbit DFT and compared against the experimental data available (only for 1 and 3). The relative binding energy calculations predict that the not yet reported s1, 2, s2, 4 and s4 complexes may be synthesized. Their optical and vibrational properties are described here. Due to the relativistic indirect effect acting on metal d orbitals there is an increased overlap between the nd and 2π* empty carbonyl orbitals, and hence the backbonding effect increases from 1/s1 to 4/s4. The calculated spin-dependent properties of the anionic complexes reveals that the isotropic g tensor decreases down the group, showing that the quenching of the total angular momentum of the unpaired electron increases along the group.",
keywords = "Group VII, Mixed valence, Pentalene, Relativistic DFT",
author = "A. Mu{\~n}oz-Castro and {Mac-Leod Carey}, D. and R. Arratia-P{\'e}rez",
year = "2009",
month = "6",
day = "10",
doi = "10.1016/j.poly.2009.03.016",
language = "English",
volume = "28",
pages = "1561--1567",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier Limited",
number = "8",

}

TY - JOUR

T1 - Electronic structure and molecular properties of binuclear group VII pentalene metal carbonyl complexes [C8H6{M(CO3)}2] (M = Mn, Tc, Re, Bh)

T2 - A relativistic density functional theory study

AU - Muñoz-Castro, A.

AU - Mac-Leod Carey, D.

AU - Arratia-Pérez, R.

PY - 2009/6/10

Y1 - 2009/6/10

N2 - Homobimetallic systems where the metals are linked through a pentalenediide ligand, of the type anti-[Pn{M(CO)3}2] (Pn = pentalenediide), which include transition metals of the group VII with M = 25Mn (1), 43Tc (2), 73Re (3) and 107Bh (4), and the syn-[Pn{M(CO)3}2] isomer with M = 25Mn (s1), 43Tc (s2), 73Re (s3) and 107Bh (s4), were studied with relativistic all-electron density functional (DFT) calculations, including spin-orbit (SO) coupling via the two components ZORA Hamiltonian. The electronic structure was studied in detail in the four systems. Broken symmetry calculations were performed for all the paramagnetic systems to verify their mixed-valence character. The infrared (IR) spectra were obtained at the scalar relativistic regime and the UV-Vis was obtained by time-dependent spin-orbit DFT and compared against the experimental data available (only for 1 and 3). The relative binding energy calculations predict that the not yet reported s1, 2, s2, 4 and s4 complexes may be synthesized. Their optical and vibrational properties are described here. Due to the relativistic indirect effect acting on metal d orbitals there is an increased overlap between the nd and 2π* empty carbonyl orbitals, and hence the backbonding effect increases from 1/s1 to 4/s4. The calculated spin-dependent properties of the anionic complexes reveals that the isotropic g tensor decreases down the group, showing that the quenching of the total angular momentum of the unpaired electron increases along the group.

AB - Homobimetallic systems where the metals are linked through a pentalenediide ligand, of the type anti-[Pn{M(CO)3}2] (Pn = pentalenediide), which include transition metals of the group VII with M = 25Mn (1), 43Tc (2), 73Re (3) and 107Bh (4), and the syn-[Pn{M(CO)3}2] isomer with M = 25Mn (s1), 43Tc (s2), 73Re (s3) and 107Bh (s4), were studied with relativistic all-electron density functional (DFT) calculations, including spin-orbit (SO) coupling via the two components ZORA Hamiltonian. The electronic structure was studied in detail in the four systems. Broken symmetry calculations were performed for all the paramagnetic systems to verify their mixed-valence character. The infrared (IR) spectra were obtained at the scalar relativistic regime and the UV-Vis was obtained by time-dependent spin-orbit DFT and compared against the experimental data available (only for 1 and 3). The relative binding energy calculations predict that the not yet reported s1, 2, s2, 4 and s4 complexes may be synthesized. Their optical and vibrational properties are described here. Due to the relativistic indirect effect acting on metal d orbitals there is an increased overlap between the nd and 2π* empty carbonyl orbitals, and hence the backbonding effect increases from 1/s1 to 4/s4. The calculated spin-dependent properties of the anionic complexes reveals that the isotropic g tensor decreases down the group, showing that the quenching of the total angular momentum of the unpaired electron increases along the group.

KW - Group VII

KW - Mixed valence

KW - Pentalene

KW - Relativistic DFT

UR - http://www.scopus.com/inward/record.url?scp=65549119594&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2009.03.016

DO - 10.1016/j.poly.2009.03.016

M3 - Article

AN - SCOPUS:65549119594

VL - 28

SP - 1561

EP - 1567

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 8

ER -