Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os6(CO)17(Au2dppm)] and [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (dppm = Ph2PCH2PPh2)

Zareen Akhter; Andrew J. Edwards; John F. Gallagher; Jack Lewis; Paul R. Raithby; Gregory P. Shields

doi:10.1016/S0022-328X(99)00695-6

Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os₆(CO)₁₇(Au₂dppm)] and [Os₆(CO)₁₇(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (dppm = Ph₂PCH₂PPh₂)

Zareen Akhter, Andrew J. Edwards, John F. Gallagher, Jack Lewis, Paul R. Raithby, Gregory P. Shields

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

13 Citations (SciVal)

Abstract

Reaction of the hexaosmium cluster [Os₆(CO)₁₈] with 1.1 equivalents of Me₃NO, in CH₂Cl₂, in the presence of one equivalent of [Au₂dppm]Cl₂ (dppm = Ph₂PCH₂PPh₂), at room temperature, affords the new mixed-metal cluster [Os₆(CO)₁₇(Au₂dppm)] (1), in high yield. Subsequent reduction of 1 with Na-Hg amalgam, and subsequent treatment with [Ru(η⁵-C₅H₅)(MeCN)₃][PF ₆] (2) afforded two decanuclear clusters [Os₆(CO)₁₇(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (3) and [Os₆(CO)₁₆(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (4) in moderate yield. Cluster 3 loses CO under reflux in toluene to produce 4. The new clusters have been fully characterised by IR, ¹H- and ³¹P-NMR spectroscopies, and mass spectrometry. The molecular and crystal structures of 1 and 3 have been established by single-crystal X-ray analyses. In 1, the bicapped tetrahedral osmium core of [Os₆(CO)₁₈] is retained and the two Au atoms of the Au2dppm group cap one Os₃ face in a μ₃-η² bonding mode. In 3 the metal core consists of a capped square-based pyramidal arrangement of Os atoms that is capped over the square face by the Au2dppm group. One Ru atom caps another face of the Os₅ square-based pyramid, and the second Ru atom caps the Ru atom, two Os atoms and an Au atom to form a trigonal bipyramidal arrangement.

Original language	English
Pages (from-to)	204-211
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	596
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(99)00695-6
Publication status	Published - 29 Feb 2000

Keywords

Carbonyl cluster
Gold
Ionic coupling
Osmium
Ruthenium
X-ray structure

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(99)00695-6

Cite this

Akhter, Z., Edwards, A. J., Gallagher, J. F., Lewis, J., Raithby, P. R., & Shields, G. P. (2000). Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os₆(CO)₁₇(Au₂dppm)] and [Os₆(CO)₁₇(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (dppm = Ph₂PCH₂PPh₂). Journal of Organometallic Chemistry, 596(1-2), 204-211. https://doi.org/10.1016/S0022-328X(99)00695-6

Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os₆(CO)₁₇(Au₂dppm)] and [Os₆(CO)₁₇(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (dppm = Ph₂PCH₂PPh₂). / Akhter, Zareen; Edwards, Andrew J.; Gallagher, John F. et al.
In: Journal of Organometallic Chemistry, Vol. 596, No. 1-2, 29.02.2000, p. 204-211.

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

Akhter, Z, Edwards, AJ, Gallagher, JF, Lewis, J, Raithby, PR & Shields, GP 2000, 'Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os₆(CO)₁₇(Au₂dppm)] and [Os₆(CO)₁₇(Au₂dppm){Ru(η⁵-C ₅H₅)}₂] (dppm = Ph₂PCH₂PPh₂)', Journal of Organometallic Chemistry, vol. 596, no. 1-2, pp. 204-211. https://doi.org/10.1016/S0022-328X(99)00695-6

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title = "Systematic formation of mixed-metal high-nuclearity clusters: The synthesis and characterisation of [Os6(CO)17(Au2dppm)] and [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (dppm = Ph2PCH2PPh2)",

abstract = "Reaction of the hexaosmium cluster [Os6(CO)18] with 1.1 equivalents of Me3NO, in CH2Cl2, in the presence of one equivalent of [Au2dppm]Cl2 (dppm = Ph2PCH2PPh2), at room temperature, affords the new mixed-metal cluster [Os6(CO)17(Au2dppm)] (1), in high yield. Subsequent reduction of 1 with Na-Hg amalgam, and subsequent treatment with [Ru(η5-C5H5)(MeCN)3][PF 6] (2) afforded two decanuclear clusters [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (3) and [Os6(CO)16(Au2dppm){Ru(η5-C 5H5)}2] (4) in moderate yield. Cluster 3 loses CO under reflux in toluene to produce 4. The new clusters have been fully characterised by IR, 1H- and 31P-NMR spectroscopies, and mass spectrometry. The molecular and crystal structures of 1 and 3 have been established by single-crystal X-ray analyses. In 1, the bicapped tetrahedral osmium core of [Os6(CO)18] is retained and the two Au atoms of the Au2dppm group cap one Os3 face in a μ3-η2 bonding mode. In 3 the metal core consists of a capped square-based pyramidal arrangement of Os atoms that is capped over the square face by the Au2dppm group. One Ru atom caps another face of the Os5 square-based pyramid, and the second Ru atom caps the Ru atom, two Os atoms and an Au atom to form a trigonal bipyramidal arrangement.",

keywords = "Carbonyl cluster, Gold, Ionic coupling, Osmium, Ruthenium, X-ray structure",

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T2 - The synthesis and characterisation of [Os6(CO)17(Au2dppm)] and [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (dppm = Ph2PCH2PPh2)

AU - Akhter, Zareen

AU - Edwards, Andrew J.

AU - Gallagher, John F.

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AU - Raithby, Paul R.

AU - Shields, Gregory P.

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N2 - Reaction of the hexaosmium cluster [Os6(CO)18] with 1.1 equivalents of Me3NO, in CH2Cl2, in the presence of one equivalent of [Au2dppm]Cl2 (dppm = Ph2PCH2PPh2), at room temperature, affords the new mixed-metal cluster [Os6(CO)17(Au2dppm)] (1), in high yield. Subsequent reduction of 1 with Na-Hg amalgam, and subsequent treatment with [Ru(η5-C5H5)(MeCN)3][PF 6] (2) afforded two decanuclear clusters [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (3) and [Os6(CO)16(Au2dppm){Ru(η5-C 5H5)}2] (4) in moderate yield. Cluster 3 loses CO under reflux in toluene to produce 4. The new clusters have been fully characterised by IR, 1H- and 31P-NMR spectroscopies, and mass spectrometry. The molecular and crystal structures of 1 and 3 have been established by single-crystal X-ray analyses. In 1, the bicapped tetrahedral osmium core of [Os6(CO)18] is retained and the two Au atoms of the Au2dppm group cap one Os3 face in a μ3-η2 bonding mode. In 3 the metal core consists of a capped square-based pyramidal arrangement of Os atoms that is capped over the square face by the Au2dppm group. One Ru atom caps another face of the Os5 square-based pyramid, and the second Ru atom caps the Ru atom, two Os atoms and an Au atom to form a trigonal bipyramidal arrangement.

AB - Reaction of the hexaosmium cluster [Os6(CO)18] with 1.1 equivalents of Me3NO, in CH2Cl2, in the presence of one equivalent of [Au2dppm]Cl2 (dppm = Ph2PCH2PPh2), at room temperature, affords the new mixed-metal cluster [Os6(CO)17(Au2dppm)] (1), in high yield. Subsequent reduction of 1 with Na-Hg amalgam, and subsequent treatment with [Ru(η5-C5H5)(MeCN)3][PF 6] (2) afforded two decanuclear clusters [Os6(CO)17(Au2dppm){Ru(η5-C 5H5)}2] (3) and [Os6(CO)16(Au2dppm){Ru(η5-C 5H5)}2] (4) in moderate yield. Cluster 3 loses CO under reflux in toluene to produce 4. The new clusters have been fully characterised by IR, 1H- and 31P-NMR spectroscopies, and mass spectrometry. The molecular and crystal structures of 1 and 3 have been established by single-crystal X-ray analyses. In 1, the bicapped tetrahedral osmium core of [Os6(CO)18] is retained and the two Au atoms of the Au2dppm group cap one Os3 face in a μ3-η2 bonding mode. In 3 the metal core consists of a capped square-based pyramidal arrangement of Os atoms that is capped over the square face by the Au2dppm group. One Ru atom caps another face of the Os5 square-based pyramid, and the second Ru atom caps the Ru atom, two Os atoms and an Au atom to form a trigonal bipyramidal arrangement.

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KW - Gold

KW - Ionic coupling

KW - Osmium

KW - Ruthenium

KW - X-ray structure

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