Unusual carbonyl and pentamethylcyclopentadienyl bonding modes in mixed rhodium-ruthenium clusters

William Clegg, Neil Feeder, Saifun Nahar, Paul R. Raithby, Gregory P. Shields, Simon J. Teat

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Thermolysis of [Ru3RhH2(CO)105-C 5Me5)], 1, in hydrocarbon solvents affords the new pentanuclear cluster [Ru3Rh23-H)μ2-CO)μ 3-CO)2(CO)6(μ-η15-CH2C5Me4)(η5-C 5Me5)], 2, together with the known complex [Ru2Rh2(CO)85-C 5Me5)2], 3. The reaction of 1 with Me3NO, in MeCN solution, followed by the immediate addition of one or two equivalents of PPh3 lead to the isolation of the mono- and di-phosphine substituted complexes [Ru3Rh(μ-H)242-CO)(μ2-CO)2(CO)6(PPh 3)(η5-C5Me5)], 4, and [Ru3Rh(μ-H)242-CO)(μ2-CO)2(CO)5(PPh 3)25-C5Me5)], 5, respectively. The new clusters have been characterised spectroscopically, and the structures of 2 and 5 established by single-crystal X-ray analyses. The metal framework in 2 is trigonal bipyramidal, with one C5Me5 ligand co-ordinated to a Rh atom in a terminal η5-bonding mode, the second cyclopentadienyl ligand has lost a methyl proton and the resultant -CH2 group is σ-bonded to one Ru atom while the C5Me4 ring is η5-bound to the adjacent Rh atom. The metal framework in 5 has opened out to give a butterfly arrangement with the Rh(η5-C5Me5) unit in one of the wing-tip positions. The butterfly is spanned by a novel μ42-bonded carbonyl ligand, and the two phosphines are terminally bound to two Ru atoms, one in a wing-tip site and the other in a hinge site.

Original languageEnglish
Pages (from-to)1111-1117
Number of pages7
JournalNew Journal of Chemistry
Volume22
Issue number10
DOIs
Publication statusPublished - Oct 1998

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

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