Osmium-antimony higher nuclearity clusters

Weng Kee Leong; Guizhu Chen

doi:10.1021/om010039s

Osmium-antimony higher nuclearity clusters

Weng Kee Leong^*, Guizhu Chen

^*Corresponding author for this work

National University of Singapore

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

37 Citations (Scopus)

Abstract

Thermolysis of Os₃(CO)₁₁(SbPh₃), 1, in refluxing octane gave initially the clusters Os₃(μ-SbPh₂)(μ-H)(μ₃,η² -C₆H₄)(CO₉), 2, and Os₆(μ₃-SbPh)(μ₃,η²-C₆H₄)(CO)₂₀, 3. Prolonged heating gave the cluster Os₆(μ₄-Sb)(μ-H)(μ₃ η⁴-C₁₂H₈) (μ₃,η²-C₆H₄)(CO)₁₆ , 4, as the major product. In contrast, thermolysis in hexane at 115 °C in a Carius tube gave Os₆(μ₄-Sb)(μ-SbPh₂)(μ-H)₂ -(μ₃,η⁴-C₁₂H₈) (μ₃,η²-C₆H₄)(CO)₁₅ , 5, Os₆(μ₄-Sb)(μ-SbPh₂)(μ-H) (μ₃,η²-C₆H₄)₂ (C₆H₅)(CO)₁₆, 6, and Os₆(μ₄-Sb)(μ-SbPh₂)(μ-H) (μ₃,η⁶-C₆H₄) (μ₃,η²-C₆H₄) (C₆H₅)(CO)₁₅, 7, besides 2 and 3. It has been demonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed from the further decomposition of 6. The reaction of 5 with SbPh₃ afforded a monosubstituted derivative, Os₆(μ₄-Sb)(μ-H)₂(μ-SbPh₂) (μ₃,η²-C₆H₄)(μ₃ ,η⁴-C₁₂H₈)(CO)₁₄ (SbPh₃), 8. The clusters 2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moiety acting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain a novel μ₃,η⁴-biphenylene moiety bound to a triosmium framework, while 7 was found to have a μ₃,η¹:η¹:η⁶ -C₆H₄ ring.

Original language	English
Pages (from-to)	2280-2287
Number of pages	8
Journal	Organometallics
Volume	20
Issue number	11
DOIs	https://doi.org/10.1021/om010039s
Publication status	Published - May 28 2001
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om010039s

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@article{e897d334b1524b2db9d8cf97721e437e,

title = "Osmium-antimony higher nuclearity clusters",

abstract = "Thermolysis of Os3(CO)11(SbPh3), 1, in refluxing octane gave initially the clusters Os3(μ-SbPh2)(μ-H)(μ3,η2 -C6H4)(CO9), 2, and Os6(μ3-SbPh)(μ3,η2-C6 H4)(CO)20, 3. Prolonged heating gave the cluster Os6(μ4-Sb)(μ-H)(μ3 η4-C12H8) (μ3,η2-C6H4)(CO)16 , 4, as the major product. In contrast, thermolysis in hexane at 115 °C in a Carius tube gave Os6(μ4-Sb)(μ-SbPh2)(μ-H)2 -(μ3,η4-C12H8) (μ3,η2-C6H4)(CO)15 , 5, Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η2-C6H4)2 (C6H5)(CO)16, 6, and Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η6-C6H4) (μ3,η2-C6H4) (C6H5)(CO)15, 7, besides 2 and 3. It has been demonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed from the further decomposition of 6. The reaction of 5 with SbPh3 afforded a monosubstituted derivative, Os6(μ4-Sb)(μ-H)2(μ-SbPh2) (μ3,η2-C6H4)(μ3 ,η4-C12H8)(CO)14 (SbPh3), 8. The clusters 2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moiety acting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain a novel μ3,η4-biphenylene moiety bound to a triosmium framework, while 7 was found to have a μ3,η1:η1:η6 -C6H4 ring.",

author = "Leong, {Weng Kee} and Guizhu Chen",

year = "2001",

month = may,

day = "28",

doi = "10.1021/om010039s",

language = "English",

volume = "20",

pages = "2280--2287",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Osmium-antimony higher nuclearity clusters

AU - Leong, Weng Kee

AU - Chen, Guizhu

PY - 2001/5/28

Y1 - 2001/5/28

N2 - Thermolysis of Os3(CO)11(SbPh3), 1, in refluxing octane gave initially the clusters Os3(μ-SbPh2)(μ-H)(μ3,η2 -C6H4)(CO9), 2, and Os6(μ3-SbPh)(μ3,η2-C6 H4)(CO)20, 3. Prolonged heating gave the cluster Os6(μ4-Sb)(μ-H)(μ3 η4-C12H8) (μ3,η2-C6H4)(CO)16 , 4, as the major product. In contrast, thermolysis in hexane at 115 °C in a Carius tube gave Os6(μ4-Sb)(μ-SbPh2)(μ-H)2 -(μ3,η4-C12H8) (μ3,η2-C6H4)(CO)15 , 5, Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η2-C6H4)2 (C6H5)(CO)16, 6, and Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η6-C6H4) (μ3,η2-C6H4) (C6H5)(CO)15, 7, besides 2 and 3. It has been demonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed from the further decomposition of 6. The reaction of 5 with SbPh3 afforded a monosubstituted derivative, Os6(μ4-Sb)(μ-H)2(μ-SbPh2) (μ3,η2-C6H4)(μ3 ,η4-C12H8)(CO)14 (SbPh3), 8. The clusters 2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moiety acting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain a novel μ3,η4-biphenylene moiety bound to a triosmium framework, while 7 was found to have a μ3,η1:η1:η6 -C6H4 ring.

AB - Thermolysis of Os3(CO)11(SbPh3), 1, in refluxing octane gave initially the clusters Os3(μ-SbPh2)(μ-H)(μ3,η2 -C6H4)(CO9), 2, and Os6(μ3-SbPh)(μ3,η2-C6 H4)(CO)20, 3. Prolonged heating gave the cluster Os6(μ4-Sb)(μ-H)(μ3 η4-C12H8) (μ3,η2-C6H4)(CO)16 , 4, as the major product. In contrast, thermolysis in hexane at 115 °C in a Carius tube gave Os6(μ4-Sb)(μ-SbPh2)(μ-H)2 -(μ3,η4-C12H8) (μ3,η2-C6H4)(CO)15 , 5, Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η2-C6H4)2 (C6H5)(CO)16, 6, and Os6(μ4-Sb)(μ-SbPh2)(μ-H) (μ3,η6-C6H4) (μ3,η2-C6H4) (C6H5)(CO)15, 7, besides 2 and 3. It has been demonstrated that cluster 6 was formed from 2, while clusters 5 and 7 were formed from the further decomposition of 6. The reaction of 5 with SbPh3 afforded a monosubstituted derivative, Os6(μ4-Sb)(μ-H)2(μ-SbPh2) (μ3,η2-C6H4)(μ3 ,η4-C12H8)(CO)14 (SbPh3), 8. The clusters 2-8 were all shown by single-crystal X-ray crystallographic studies to have a benzyne moiety acting as a four-electron donor to a triosmium fragment. In addition, 4 and 8 contain a novel μ3,η4-biphenylene moiety bound to a triosmium framework, while 7 was found to have a μ3,η1:η1:η6 -C6H4 ring.

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DO - 10.1021/om010039s

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ER -

Osmium-antimony higher nuclearity clusters

Abstract

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