Metal core rearrangements in hetero-bimetallic nona-osmium carbonyl clusters; the crystal and molecular structures of [Os9(CO)24{Au(PCy3i)}2] and [Os9(CO)23(Au2DPPE)]

Zareen Akhter, Scott L. Ingham, Jack Lewis, Paul R. Raithby

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The reaction of the nona-osmium cluster dianion [(Ph3P)2N]2[Os9(CO)24] with the electrophilic gold reagents "AuPR+3" and "Au2L2+" (where R = Ph (2a, 3a), Cy (2b, 3b) and L = bis-(diphenylphosphino)methane (DPPM) (1a) or 1,2-bis-(diphenyl)ethane (DPPE) (1b)) has been studied. The monogold fragment reacts to give both the mono- and di-substituted products [(Ph3P)2N][Os9(CO)24{Au(PR 3)}2] and [Os9(CO)24{Au(PR3)}2]. The structure of the latter cluster (R = Cy (2b)) has been determined by a single crystal X-ray diffraction analysis and a major rearrangement of the metal core geometry was found to have occurred on coordination of the gold fragments. In contrast, reaction with the digold reagent "Au2L2+" results in the isolation of only one product of formulation [Os9(CO)23(Au2L)], where coordination of the heteroatom moiety has been accompanied with the loss of a carbonyl ligand. From a single crystal X-ray diffraction analysis (L = DPPE (1b)) this compound was shown to have retained its original cluster geometry, with the gold atoms coordinated in close proximity to each other.

Original languageEnglish
Pages (from-to)131-139
Number of pages9
JournalJournal of Organometallic Chemistry
Volume550
Issue number1-2
DOIs
Publication statusPublished - 15 Jan 1998

Keywords

  • Cluster carbonyls
  • Gold
  • Osmium
  • Phosphines
  • X-ray structure

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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