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 journalArticle

13 Citations (Scopus)

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 μ32 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 languageEnglish
Pages (from-to)204-211
Number of pages8
JournalJournal of Organometallic Chemistry
Volume596
Issue number1-2
DOIs
Publication statusPublished - 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

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