X-ray structure, reactivity, and catalytic properties of a (cyclopentadienone)ruthenium dimer, [(C4Ph4CO)(CO)2Ru]2

Martin J. Mays, Michael J. Morris, Paul R. Raithby, Youval Shvo, Dorotha Czarkie

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The title complex 4a as well as several other isostructural complexes have been prepared. Single-crystal X-ray diffraction analysis of 4a indicates a centrosymmetric dimeric structure (Figure 1); the complex crystallizes in space group P1 (No. 2): a = 10.938 (1) Å, b = 11.990 (1) Å, c = 12.528 (1) Å, α = 68.62 (1)°, β = 77.99 (1)°, γ = 64.18 (1)°, V = 1374.8 (2) Å3, Z = 2 (monomer units), 4835 unique reflections, R = 0.056, 4324 reflections, F > 4σ(F). The cyclopentadienone carbonyl is bent back from the diene plane at an angle of 6.7°, with a >C=0 bond length of 1.270 (7) Å. A crossover experiment with two structurally different dimer complexes indicates that the thermal dissociation of these dimers is a relatively low-energy process. Nucleophilic ligands, L (L = CO, phosphines, amines), react readily with 4a to give mononuclear complexes of the type (η4-C4Ph4CO)Ru(CO)2L. Treatment of 4a with either dihydrogen or ethanol leads to oxidative addition of dihydrogen to Ru with the formation of (η5-C4Ph4COH)(CO)2RuH. The catalytic activity of 4a and other related complexes is discussed in the light of the above results.

Original languageEnglish
Pages (from-to)1162-1167
Number of pages6
Issue number5
Publication statusPublished - 1 May 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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