Synthesis and characterisation of phosphido-bridged hexaosmium "raft" clusters; crystal structure of OS6H2(CO)183-PPh)

Caroline M. Hay, John G. Jeffrey, Brian F.G. Johnson, Jack Lewis, Paul R. Raithby

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Treatment of the activated "raft" cluster Os6(CO)20(NCMe) with PR1R2H (R1R2Ph; R1Ph, R2H) at room temperature affords the phosphine-substituted cluster Os6(CO)20(PR1R2H) (R1R2Ph (1); R1Ph, R2H (1)) in quantitative yield. Thermolysis of 1 in toluene gives a single orange-brown product characterised as Os6(CO)16(μ-PPhO2) (3). This complex is also obtained from the thermolysis of Os6(CO)17(PPh2H), which has the bicapped tetrahedral metal framework. Thermolysis of 2 gives two products, characterised as Os6H2(CO)183-PPh) (4) and the known complex Os5(CO)154-PPh) (5). The structure of 4 has been established by a single-crystal X-ray diffraction study. The metal framework consists of a central Os3 triangle each side of which is bridged by another Os atom to give an arrangement of four triangles sharing three common edges. Three of these triangles are approximately coplanar, but the fourth, which is asymmetrically capped by the phosphorus atom of the μ3-PPh group, is tilted by 72.4° from the Os5 plane. Complex 4 crystallises in space group P 1 - with a 9.733(2), b 10.555(1), c 17.585(2) Å, α 95.87(1), β 94.47(2), γ 105.60(1)°, Z = 2; 4591 observed data with F > 4σ(F) were refined by blocked full-matrix least squares to R = 0.080, Rw = 0.079.

Original languageEnglish
Pages (from-to)87-96
Number of pages10
JournalJournal of Organometallic Chemistry
Issue number1
Publication statusPublished - 3 Jan 1989

ASJC Scopus subject areas

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

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