Synthesis of triosmium alkylidyne clusters incorporating bis(diphenylphosphino) alkane type ligands. Crystal structures of [{Os3(μ-H)2(CO) 9(μ3-C)}2(μ-dpp)] (dppp = bis(diphenylphosphino)propane) and [Os3(μ-H)2(CO) 8(μ3-CPPh2CH2PPh2)]

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Abstract

The reaction of triosmium alkylidyne cluster [Os3(μ-H)3(CO)9(μ3-CCI)] with excess bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)propane (dppp) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) yields [Os3(μ-H)2(CO)9(μ3-CPPh2CH2PPh2)] 1, [Os3(μ-H)2(CO)9(μ3-CPPh2CH2CH2PPh2)] 2, and a linking cluster [{Os3(μ-H)2(CO)9(μ3-C)}2(μ-dppp)] 3 respectively in moderate yields. Complexes 1 and 2 are found to undergo ring formation by decarbonylation and formation of an Os-P bond to give new clusters [Os3(μ-H)2(CO)8(μ3-CPPh2CH2)PPh2] 4 and [Os3(μ-H)2(CO)8(μ3--CPPh2CH2CH2)PPh2] 5. Single-crystal X-ray structural analyses of 3 and 4 have shown that there was a phosphine-substituted μ3-C ligand bonded to one of the triosmium metal cores, giving a five-membered osmacycle complex for 4, while 3 has the structure of a linking cluster, with the two triosmium alkylidyne cluster units linked by a dppp ligand.
Original languageEnglish
Pages (from-to)227-233
Number of pages7
JournalJournal of Organometallic Chemistry
Volume518
Issue number1-2
DOIs
Publication statusPublished - 12 Jul 1996
Externally publishedYes

Keywords

  • Alkylidyne
  • Bis(diphenylphosphino)alkane
  • Carbonyl
  • Clusters
  • Crystal structure
  • Osmium

ASJC Scopus subject areas

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

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