A Five-Coordinated d6 Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium(II)

Sam J. La Placa, James A. Ibers

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289 Scopus citations


A complete X-ray structure determination of dichlorotris(triphenylphosphine)ruthenium(II), RuCl2[P(C6H5)3]3, has been carried out in order to ascertain if in this compound the Ru(II) (d6) is five-coordinated. The compound crystallizes in space group C2h 5-P21/c of the monoclinic system in a cell of dimensions a = 18.01, b = 20.22, c = 12.36 A., /3 = 90.5°. The observed density is 1.43 g./cm.3, and the density calculated for four molecules in the cell is 1.415 g./cm.3. There are no crystallographic symmetry conditions imposed on the molecule. The structure consists of the packing of individual monomeric molecules. In these molecules the Ru lies toward the center of a distorted square pyramid which consists of trans CI atoms and trans P atoms in the base and an apical P atom. The apical Ru-P distance of 2.23 A. is about 0.16 A. shorter than the basal Ru-P distances. This is the only known example from X-ray structural studies of a five-coordinated d6 complex, and it probably occurs not because of an inherent tendency toward five-coordination, but rather because the unused octahedral site about the square-pyramidal configuration is effectively blocked by a phenyl ring.

Original languageEnglish (US)
Pages (from-to)778-783
Number of pages6
JournalInorganic Chemistry
Issue number6
StatePublished - Jun 1 1965

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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