Ligand substitution in the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10

Padmamalini Srinivasan; Weng Kee Leong

doi:10.1016/j.jorganchem.2005.09.036

Ligand substitution in the heterometallic cluster Cp*IrOs ₃(μ-H)₂(CO)₁₀

Padmamalini Srinivasan, Weng Kee Leong^*

^*Corresponding author for this work

National University of Singapore

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

1 Citation (Scopus)

Abstract

The reactions of the heterometallic cluster Cp*IrOs ₃(μ-H)₂(CO)₁₀ with phosphines, isonitriles and pyridine under TMNO activation afforded the substitution products Cp*IrOs₃(μ-H)₂(CO)_10-nL_n (n = 1, 2; L = PPh₃, P(OMe)₃, ^tBuNC, CyNC or py) in good yields. For the monosubstituted derivatives, the substitution site was exclusively at an osmium atom in an axial position for L = phosphine or phosphite. Spectroscopic evidence suggested the presence of isomers in solution for the PPh₃ derivative. In contrast, for L = isonitrile, the ligand occupied an equatorial site. In the disubstituted derivatives, the group 15 ligands were coordinated to two different osmium atoms, one each at an axial and an equatorial site. The isomerism and fluxional behaviour of some of these clusters have also been examined.

Original language	English
Pages (from-to)	371-379
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	691
Issue number	3
DOIs	https://doi.org/10.1016/j.jorganchem.2005.09.036
Publication status	Published - Jan 15 2006
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Cluster
Fluxional
Heteronuclear
Iridium
Isonitrile
Osmium
Phosphine
Ruthenium

Access to Document

10.1016/j.jorganchem.2005.09.036

Cite this

@article{79fd3bdecc6b46579234169d119bd4e1,

title = "Ligand substitution in the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10",

abstract = "The reactions of the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10 with phosphines, isonitriles and pyridine under TMNO activation afforded the substitution products Cp*IrOs3(μ-H)2(CO)10-nLn (n = 1, 2; L = PPh3, P(OMe)3, tBuNC, CyNC or py) in good yields. For the monosubstituted derivatives, the substitution site was exclusively at an osmium atom in an axial position for L = phosphine or phosphite. Spectroscopic evidence suggested the presence of isomers in solution for the PPh3 derivative. In contrast, for L = isonitrile, the ligand occupied an equatorial site. In the disubstituted derivatives, the group 15 ligands were coordinated to two different osmium atoms, one each at an axial and an equatorial site. The isomerism and fluxional behaviour of some of these clusters have also been examined.",

keywords = "Cluster, Fluxional, Heteronuclear, Iridium, Isonitrile, Osmium, Phosphine, Ruthenium",

author = "Padmamalini Srinivasan and Leong, {Weng Kee}",

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T1 - Ligand substitution in the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10

AU - Srinivasan, Padmamalini

AU - Leong, Weng Kee

PY - 2006/1/15

Y1 - 2006/1/15

N2 - The reactions of the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10 with phosphines, isonitriles and pyridine under TMNO activation afforded the substitution products Cp*IrOs3(μ-H)2(CO)10-nLn (n = 1, 2; L = PPh3, P(OMe)3, tBuNC, CyNC or py) in good yields. For the monosubstituted derivatives, the substitution site was exclusively at an osmium atom in an axial position for L = phosphine or phosphite. Spectroscopic evidence suggested the presence of isomers in solution for the PPh3 derivative. In contrast, for L = isonitrile, the ligand occupied an equatorial site. In the disubstituted derivatives, the group 15 ligands were coordinated to two different osmium atoms, one each at an axial and an equatorial site. The isomerism and fluxional behaviour of some of these clusters have also been examined.

AB - The reactions of the heterometallic cluster Cp*IrOs 3(μ-H)2(CO)10 with phosphines, isonitriles and pyridine under TMNO activation afforded the substitution products Cp*IrOs3(μ-H)2(CO)10-nLn (n = 1, 2; L = PPh3, P(OMe)3, tBuNC, CyNC or py) in good yields. For the monosubstituted derivatives, the substitution site was exclusively at an osmium atom in an axial position for L = phosphine or phosphite. Spectroscopic evidence suggested the presence of isomers in solution for the PPh3 derivative. In contrast, for L = isonitrile, the ligand occupied an equatorial site. In the disubstituted derivatives, the group 15 ligands were coordinated to two different osmium atoms, one each at an axial and an equatorial site. The isomerism and fluxional behaviour of some of these clusters have also been examined.

KW - Cluster

KW - Fluxional

KW - Heteronuclear

KW - Iridium

KW - Isonitrile

KW - Osmium

KW - Phosphine

KW - Ruthenium

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