Ligand substitution in the osmium-antimony rings Os3(μ-SbPh2)2(CO)10and Os3(μ-SbPh2)3(Cl)(CO)9

Ying Zhou Li; Rakesh Ganguly; Weng Kee Leong

doi:10.1016/j.jorganchem.2016.07.028

Ligand substitution in the osmium-antimony rings Os₃(μ-SbPh₂)₂(CO)₁₀and Os₃(μ-SbPh₂)₃(Cl)(CO)₉

Ying Zhou Li, Rakesh Ganguly, Weng Kee Leong^*

^*Corresponding author for this work

Nanyang Technological University

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

9 Citations (Scopus)

Abstract

TMNO-activated ligand substitution in the fused ring compounds Os₃(μ-SbPh₂)₂(CO)₁₀, 1, and Os₃(μ-SbPh₂)₃(Cl)(CO)₉, 2, in acetonitrile affords the mono- and disubstituted CH₃CN-derivatives. The initial product of CH₃CN substitution in 1 is an equatorial isomer, which can isomerize to the axial isomer upon heating; they are the first examples in which both isomers have been characterized crystallographically. Subsequent reaction of the CH₃CN-derivatives of 2 with two-electron donor ligands L do not always result in the displacement of the acetonitrile ligands; displacement of a carbonyl ligand can also occur and appears to depend on the stereoelectronic properties of L. This is suggestive of an associative mechanism.

Original language	English
Pages (from-to)	46-54
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	820
DOIs	https://doi.org/10.1016/j.jorganchem.2016.07.028
Publication status	Published - 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2016 Elsevier B.V.

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Antimony
Carbonyl clusters
Ligand substitution
Osmium

Access to Document

10.1016/j.jorganchem.2016.07.028

Cite this

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title = "Ligand substitution in the osmium-antimony rings Os3(μ-SbPh2)2(CO)10and Os3(μ-SbPh2)3(Cl)(CO)9",

abstract = "TMNO-activated ligand substitution in the fused ring compounds Os3(μ-SbPh2)2(CO)10, 1, and Os3(μ-SbPh2)3(Cl)(CO)9, 2, in acetonitrile affords the mono- and disubstituted CH3CN-derivatives. The initial product of CH3CN substitution in 1 is an equatorial isomer, which can isomerize to the axial isomer upon heating; they are the first examples in which both isomers have been characterized crystallographically. Subsequent reaction of the CH3CN-derivatives of 2 with two-electron donor ligands L do not always result in the displacement of the acetonitrile ligands; displacement of a carbonyl ligand can also occur and appears to depend on the stereoelectronic properties of L. This is suggestive of an associative mechanism.",

keywords = "Antimony, Carbonyl clusters, Ligand substitution, Osmium",

author = "Li, {Ying Zhou} and Rakesh Ganguly and Leong, {Weng Kee}",

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language = "English",

volume = "820",

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T1 - Ligand substitution in the osmium-antimony rings Os3(μ-SbPh2)2(CO)10and Os3(μ-SbPh2)3(Cl)(CO)9

AU - Li, Ying Zhou

AU - Ganguly, Rakesh

AU - Leong, Weng Kee

PY - 2016

Y1 - 2016

N2 - TMNO-activated ligand substitution in the fused ring compounds Os3(μ-SbPh2)2(CO)10, 1, and Os3(μ-SbPh2)3(Cl)(CO)9, 2, in acetonitrile affords the mono- and disubstituted CH3CN-derivatives. The initial product of CH3CN substitution in 1 is an equatorial isomer, which can isomerize to the axial isomer upon heating; they are the first examples in which both isomers have been characterized crystallographically. Subsequent reaction of the CH3CN-derivatives of 2 with two-electron donor ligands L do not always result in the displacement of the acetonitrile ligands; displacement of a carbonyl ligand can also occur and appears to depend on the stereoelectronic properties of L. This is suggestive of an associative mechanism.

AB - TMNO-activated ligand substitution in the fused ring compounds Os3(μ-SbPh2)2(CO)10, 1, and Os3(μ-SbPh2)3(Cl)(CO)9, 2, in acetonitrile affords the mono- and disubstituted CH3CN-derivatives. The initial product of CH3CN substitution in 1 is an equatorial isomer, which can isomerize to the axial isomer upon heating; they are the first examples in which both isomers have been characterized crystallographically. Subsequent reaction of the CH3CN-derivatives of 2 with two-electron donor ligands L do not always result in the displacement of the acetonitrile ligands; displacement of a carbonyl ligand can also occur and appears to depend on the stereoelectronic properties of L. This is suggestive of an associative mechanism.

KW - Antimony

KW - Carbonyl clusters

KW - Ligand substitution

KW - Osmium

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