Influence of the ligand on the coupling between the metal-based electrons in face-shared [M2X9]3- (M = Mo, W; X = F, Cl, Br, I) systems

Germán Cavigliasso; Robert Stranger

doi:10.1021/ic026291p

Influence of the ligand on the coupling between the metal-based electrons in face-shared [M₂X₉]^3- (M = Mo, W; X = F, Cl, Br, I) systems

Germán Cavigliasso, Robert Stranger^*

^*Corresponding author for this work

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

9 Citations (Scopus)

Abstract

Orbital overlap and spin polarization effects in Mo and W [M ₂X₉]^3- halide and in [M ₂X′₃X″6]^3- mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M ₂X₉]^3- systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M₂X′ ₃X″6]^3- systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.

Original language	English
Pages (from-to)	5252-5258
Number of pages	7
Journal	Inorganic Chemistry
Volume	42
Issue number	17
DOIs	https://doi.org/10.1021/ic026291p
Publication status	Published - 25 Aug 2003

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abstract = "Orbital overlap and spin polarization effects in Mo and W [M 2X9]3- halide and in [M 2X′3X″6]3- mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M 2X9]3- systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M2X′ 3X″6]3- systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.",

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AU - Stranger, Robert

PY - 2003/8/25

Y1 - 2003/8/25

N2 - Orbital overlap and spin polarization effects in Mo and W [M 2X9]3- halide and in [M 2X′3X″6]3- mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M 2X9]3- systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M2X′ 3X″6]3- systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.

AB - Orbital overlap and spin polarization effects in Mo and W [M 2X9]3- halide and in [M 2X′3X″6]3- mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M 2X9]3- systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M2X′ 3X″6]3- systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.

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Influence of the ligand on the coupling between the metal-based electrons in face-shared [M₂X₉]^3- (M = Mo, W; X = F, Cl, Br, I) systems

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