Synthetic Studies on the CpRu-PPh3-(Se2) System: Redox Interconversions of Ru2(Se2)2 Cores

Jayantha Amarasekera, Eric J. Houser, Thomas B. Rauchfuss, Charlotte L. Stern

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The reaction of NaSeH and CpRu(PPh3)2Cl gave CpRu(PPh3)2SeH, while the synthesis of (MeCp)Ru(PPh3)2SeH required the use of NMe4SeH. The corresponding H2Se complexes could not be prepared, as CpRu(PPh3)2OTf failed to add H2Se and protonation of (MeCp)Ru(PPh3)2SeH gave (MeCp)Ru(PPh3)2H2+. The reaction of CpRu(PPh3)2OTf with elemental selenium gave [CpRu(PPh3)2]2(μ-η 11-Se2)(OTf)2 (1). The compound 1·PhMe·CH2Cl2 crystallized in the monoclinic space group P21, with a = 15.965 (3) Å, b = 15.898 (5) Å, c = 18.406 (4) Å, α = γ = 90°, β = 111.28 (2)°, V = 4353 (3) Å3, and Z = 2. The structure was refined to R = 0.054 (Rw = 0.061). The crystallographic studies provide evidence for Ru-Se multiple bonding but show that the Ru2Se2 core is not planar, unlike the core of the analogous persulfido complex. Solutions of 1 reacted further with selenium to give primarily [CpRu(PPh3)]2(μ-η12-Se2)2(OTf)2. The analogous MeCp complex (2) was characterized by X-ray crystallography. It crystallizes in the triclinic space group P1, with a = 10.909 (5) Å, b = 13.530 (5) Å, c = 10.064 (4) Å, α = 110.13 (3)°, β = 112.18 (3)°, γ = 79.62 (3)°, V = 1289 (2) A3, and Z = 1. The structure was refined to R = 0.050 (Rw = 0.058). Compound 2 was reduced by Cp2Co to give the unstable compound [(MeCp)Ru(PPh3)]2(μ-η11-Se2)2, which could be reoxidized to give 2 and which in turn thermally eliminated SePPh3 to give (MeCp)4Ru4Se4.

Original languageEnglish (US)
Pages (from-to)1614-1620
Number of pages7
JournalInorganic Chemistry
Issue number9
StatePublished - Apr 1 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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