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

Funding

We gratefully acknowledge the Cambridge Commonwealth Trust and the UK Committee of Vice Chancellors and Principals (Z.A.), the European Union (J.F.G.), the Engineering and Physical Sciences Research Council (A.J.E.) and the Cambridge Crystallographic Data Centre (G.P.S.) for financial support. We also thank the EPSRC for funding the purchase of X-ray equipment and Johnson–Matthey for the generous loan of heavy metal salts.

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.",

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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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