Synthesis, Structure, and Molecular Orbital Calculation of the Bicapped Triangular Molybdenum Cluster Complex [Mo3S5(PMe3)6]

Kiyoshi Tsuge; Hideo Imoto; Taro Saito

doi:10.1021/ic00117a006

Synthesis, Structure, and Molecular Orbital Calculation of the Bicapped Triangular Molybdenum Cluster Complex [Mo₃S₅(PMe₃)₆]

Kiyoshi Tsuge, Hideo Imoto, Taro Saito^*

^*Corresponding author for this work

Department of Chemistry

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

20 Scopus citations

Abstract

Treatment of the sulfur monocapped molybdenum trinuclear cluster (NH₄)₂[Mo₃S₁₃] with excess trimethylphosphine affords the sulfur bicapped molybdenum trinuclear cluster complex [Mo₃(μ₃-S)₂(μ₂-S)₃(PMe₃)6]. This compound crystallizes in the rhombohedral space group R3c with a = 11.112(1) Å, c = 53.507(10) Å, V = 5722(1) Å, Z = 6, R = 0.043, and R_w = 0.026. The Mo₃ triangle is equilateral with the Mo-Mo distance 2.714(1) Å. Calculations by the DV-Xa method on this compound show that the structural difference from an isoelectronic cluster anion [Mo₃S₂Cl₉]³⁻ is caused by the reversal of the HOMO and LUMO. Calculated populations and a qualitative molecular orbital discussion reveal that this reversal is due to the p antibonding interaction between the metal atoms and bridging ligands. Construction of qualitative MOs clarifies the effect of the M-L p interaction on the MOs derived from metal t_2g orbitals in the M₃X₅L₆-type and M₃X₄L₉-type clusters where metal atoms are in the octahedral coordination.

Original language	English
Pages (from-to)	3404-3409
Number of pages	6
Journal	Inorganic Chemistry
Volume	34
Issue number	13
DOIs	https://doi.org/10.1021/ic00117a006
State	Published - 1995/06/01

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00117a006

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@article{9143a31f2a5840778aa0a1fce194c5b0,

title = "Synthesis, Structure, and Molecular Orbital Calculation of the Bicapped Triangular Molybdenum Cluster Complex [Mo3S5(PMe3)6]",

abstract = "Treatment of the sulfur monocapped molybdenum trinuclear cluster (NH4)2[Mo3S13] with excess trimethylphosphine affords the sulfur bicapped molybdenum trinuclear cluster complex [Mo3(μ3-S)2(μ2-S)3(PMe3)6]. This compound crystallizes in the rhombohedral space group R3c with a = 11.112(1) {\AA}, c = 53.507(10) {\AA}, V = 5722(1) {\AA}, Z = 6, R = 0.043, and Rw = 0.026. The Mo3 triangle is equilateral with the Mo-Mo distance 2.714(1) {\AA}. Calculations by the DV-Xa method on this compound show that the structural difference from an isoelectronic cluster anion [Mo3S2Cl9]3− is caused by the reversal of the HOMO and LUMO. Calculated populations and a qualitative molecular orbital discussion reveal that this reversal is due to the p antibonding interaction between the metal atoms and bridging ligands. Construction of qualitative MOs clarifies the effect of the M-L p interaction on the MOs derived from metal t2g orbitals in the M3X5L6-type and M3X4L9-type clusters where metal atoms are in the octahedral coordination.",

author = "Kiyoshi Tsuge and Hideo Imoto and Taro Saito",

year = "1995",

month = jun,

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doi = "10.1021/ic00117a006",

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journal = "Inorganic Chemistry",

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T1 - Synthesis, Structure, and Molecular Orbital Calculation of the Bicapped Triangular Molybdenum Cluster Complex [Mo3S5(PMe3)6]

AU - Tsuge, Kiyoshi

AU - Imoto, Hideo

AU - Saito, Taro

PY - 1995/6/1

Y1 - 1995/6/1

N2 - Treatment of the sulfur monocapped molybdenum trinuclear cluster (NH4)2[Mo3S13] with excess trimethylphosphine affords the sulfur bicapped molybdenum trinuclear cluster complex [Mo3(μ3-S)2(μ2-S)3(PMe3)6]. This compound crystallizes in the rhombohedral space group R3c with a = 11.112(1) Å, c = 53.507(10) Å, V = 5722(1) Å, Z = 6, R = 0.043, and Rw = 0.026. The Mo3 triangle is equilateral with the Mo-Mo distance 2.714(1) Å. Calculations by the DV-Xa method on this compound show that the structural difference from an isoelectronic cluster anion [Mo3S2Cl9]3− is caused by the reversal of the HOMO and LUMO. Calculated populations and a qualitative molecular orbital discussion reveal that this reversal is due to the p antibonding interaction between the metal atoms and bridging ligands. Construction of qualitative MOs clarifies the effect of the M-L p interaction on the MOs derived from metal t2g orbitals in the M3X5L6-type and M3X4L9-type clusters where metal atoms are in the octahedral coordination.

AB - Treatment of the sulfur monocapped molybdenum trinuclear cluster (NH4)2[Mo3S13] with excess trimethylphosphine affords the sulfur bicapped molybdenum trinuclear cluster complex [Mo3(μ3-S)2(μ2-S)3(PMe3)6]. This compound crystallizes in the rhombohedral space group R3c with a = 11.112(1) Å, c = 53.507(10) Å, V = 5722(1) Å, Z = 6, R = 0.043, and Rw = 0.026. The Mo3 triangle is equilateral with the Mo-Mo distance 2.714(1) Å. Calculations by the DV-Xa method on this compound show that the structural difference from an isoelectronic cluster anion [Mo3S2Cl9]3− is caused by the reversal of the HOMO and LUMO. Calculated populations and a qualitative molecular orbital discussion reveal that this reversal is due to the p antibonding interaction between the metal atoms and bridging ligands. Construction of qualitative MOs clarifies the effect of the M-L p interaction on the MOs derived from metal t2g orbitals in the M3X5L6-type and M3X4L9-type clusters where metal atoms are in the octahedral coordination.

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