Electronic structure and bonding of the [W6S8(CN) 6]6- cluster anion

Rosario Sienra Muraña; Lucia Hernandez-Acevedo; Ramiro Arratia-Pérez

doi:10.1016/j.cplett.2004.06.059

Electronic structure and bonding of the [W₆S₈(CN) ₆]^6- cluster anion

Rosario Sienra Muraña, Lucia Hernandez-Acevedo, Ramiro Arratia-Pérez

Facultad Ciencias Exactas

Resultado de la investigación: Contribución a una revista › Artículo › revisión exhaustiva

Resumen

Dirac-Slater multiple scattering and its non-relativistic limit calculations on the reduced octahedral (20e) [W₆S₈(CN) ₆]^6- cluster ion are reported. The non-relativistic limit calculations predict a paramagnetic cluster with a triplet ground state, while the relativistic calculations predict a diamagnetic cluster with a singlet ground state, which is in agreement with the single sharp signal seen in ¹³C NMR experiments in deoxygenated D₂O at room temperature. We have also calculated the relativistic electronic structure of the oxidized 19e [W₆S₈(CN)₆]^5- cluster ion. The calculated relativistic local density of states at the Fermi level of the [W₆S₈(CN)₆]^6- cluster ion differs from those calculated for the 24e [Re₆S ₈(CN)₆]^4- cluster ion. This may explain the different role played by the axial cyanide ligands in their cluster reactivities.

Idioma original	Inglés
Páginas (desde-hasta)	277-281
Número de páginas	5
Publicación	Chemical Physics Letters
Volumen	393
N.º	1-3
DOI	https://doi.org/10.1016/j.cplett.2004.06.059
Estado	Publicada - 21 jul. 2004

Áreas temáticas de ASJC Scopus

Física y astronomía (todo)
Química física y teórica

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10.1016/j.cplett.2004.06.059

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title = "Electronic structure and bonding of the [W6S8(CN) 6]6- cluster anion",

abstract = "Dirac-Slater multiple scattering and its non-relativistic limit calculations on the reduced octahedral (20e) [W6S8(CN) 6]6- cluster ion are reported. The non-relativistic limit calculations predict a paramagnetic cluster with a triplet ground state, while the relativistic calculations predict a diamagnetic cluster with a singlet ground state, which is in agreement with the single sharp signal seen in 13C NMR experiments in deoxygenated D2O at room temperature. We have also calculated the relativistic electronic structure of the oxidized 19e [W6S8(CN)6]5- cluster ion. The calculated relativistic local density of states at the Fermi level of the [W6S8(CN)6]6- cluster ion differs from those calculated for the 24e [Re6S 8(CN)6]4- cluster ion. This may explain the different role played by the axial cyanide ligands in their cluster reactivities.",

author = "{Sienra Mura{\~n}a}, Rosario and Lucia Hernandez-Acevedo and Ramiro Arratia-P{\'e}rez",

note = "Funding Information: This work has been supported by Fondecyt No. 1030148, UNAB-DI 10-02, and the Millenium Nucleus of Applied Quantum Mechanics and Computational Chemistry, P02-004-F.",

year = "2004",

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doi = "10.1016/j.cplett.2004.06.059",

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AU - Sienra Muraña, Rosario

AU - Hernandez-Acevedo, Lucia

AU - Arratia-Pérez, Ramiro

N1 - Funding Information: This work has been supported by Fondecyt No. 1030148, UNAB-DI 10-02, and the Millenium Nucleus of Applied Quantum Mechanics and Computational Chemistry, P02-004-F.

PY - 2004/7/21

Y1 - 2004/7/21

N2 - Dirac-Slater multiple scattering and its non-relativistic limit calculations on the reduced octahedral (20e) [W6S8(CN) 6]6- cluster ion are reported. The non-relativistic limit calculations predict a paramagnetic cluster with a triplet ground state, while the relativistic calculations predict a diamagnetic cluster with a singlet ground state, which is in agreement with the single sharp signal seen in 13C NMR experiments in deoxygenated D2O at room temperature. We have also calculated the relativistic electronic structure of the oxidized 19e [W6S8(CN)6]5- cluster ion. The calculated relativistic local density of states at the Fermi level of the [W6S8(CN)6]6- cluster ion differs from those calculated for the 24e [Re6S 8(CN)6]4- cluster ion. This may explain the different role played by the axial cyanide ligands in their cluster reactivities.

AB - Dirac-Slater multiple scattering and its non-relativistic limit calculations on the reduced octahedral (20e) [W6S8(CN) 6]6- cluster ion are reported. The non-relativistic limit calculations predict a paramagnetic cluster with a triplet ground state, while the relativistic calculations predict a diamagnetic cluster with a singlet ground state, which is in agreement with the single sharp signal seen in 13C NMR experiments in deoxygenated D2O at room temperature. We have also calculated the relativistic electronic structure of the oxidized 19e [W6S8(CN)6]5- cluster ion. The calculated relativistic local density of states at the Fermi level of the [W6S8(CN)6]6- cluster ion differs from those calculated for the 24e [Re6S 8(CN)6]4- cluster ion. This may explain the different role played by the axial cyanide ligands in their cluster reactivities.

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