Syntheses and characterization of the ruthenium carbonyl porphyrin complexes Ru(TPP)(CO)(1-MeIm) and Ru(α-PocPivP)(CO)(1-MeIm)

Carla Slebodnick, Won K. Seok, Kimoon Kim, James A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


Ru(TPP)(CO)(1-MeIm) and Ru(α-PocPivP)(CO)(1-MeIm) (TPP = tetraphenylporphyrinato; PocPivP = 'pocket' porphyrin dianion) were prepared by metalation of the free-base porphyrins with Ru3(CO)12, followed by reaction with 1-MeIm. The structures of Ru(TPP)(CO)(1-MeIm) and Ru(α-PocPivP)(CO)(1-MeIm) have been determined by single-crystal X-ray diffraction methods. The compound Ru(TPP)(CO)(1-MeIm) packs as one crystallographically independent porphyrin molecule with toluene solvate, whereas Ru(α-PocPivP)(CO)(1-MeIm) crystallizes as two crystallographically independent porphyrin molecules, molecule A and molecule B, with disordered solvate, modeled as water. In Ru(TPP)(CO)(1-MeIm) the Ru atom lies 0.032 Å out of the 24-atom porphyrin plane toward the CO ligand. The Ru-C-O bond angle is 179.3(2)° and the Ru-C(CO) and C-O bond distances are 1.828(2) Å and 1.147(3) Å, respectively. The Ru-Nax(1-MeIm) distance is 2.187(2) Å, compared with an average Ru-Neq(porphine) distance of 2.058(3) Å. The molecular structure of Ru(α-PocPivP)(CO)(1-MeIm), a sterically protected 'pocket' porphyrin, is more distorted than that of Ru(TPP)(CO)(1-MeIm). In molecule A the Ru atom lies 0.03 Å out of the 24-atom porphyrin plane toward the 1-MeIm ligand whereas in molecule B the Ru atom lies 0.01 Å out of the porphyrin plane toward the CO ligand. For molecule A the Ru-C(CO) and C-O bond distances are 1.82(3) Å and 1.18(3) Å, respectively, and the Ru-C-O bond angle is 168(3)°. Respective values for molecule B are 1.82(2) Å, 1.16(3) Å, and 159(3)°. The M-Nax distances are 2.20(2) Å and 2.16(2) Å, respectively, for molecules A and B. The average M-Neq distances are 2.03(3) Å and 2.03(5) Å. The CO stretching frequencies are 1939cm-1 for Ru(TPP)(CO)(1-MeIm) and 1933cm-1 for Ru(α-PocPivP)(CO)(1-MeIm). Crystallographic data for Ru(TPP)(CO)(1-MeIm): triclinic, Ci1-P1̄, Z = 2, a = 9.796(2) Å, b = 13.320(1) Å, c = 17.618(2) Å, α = 74.88(1)°, β = 87.97(1)°, γ = 83.23(1)°, Τ = 153 K, 9049 unique reflections, 579 variables, R(F) (Fo2 > 2σ(Fo2)) = 0.034, Rw(F2) = 0.094. Crystallographic data for Ru(α-PocPivP)(CO)(1-MeIm): orthorhombic, C2v9-Pn21a, Z = 8, a = 26.672(5) Å, b = 32.243(6) Å, c = 14.124(3) Å, Τ = 150 K, 8006 unique reflections, 699 variables, R(F) (Fo2 > 2σ(Fo2)) = 0.113, Rw(F2) = 0.246.

Original languageEnglish (US)
Pages (from-to)57-65
Number of pages9
JournalInorganica Chimica Acta
Issue number1-2
StatePublished - Feb 29 1996


  • Carbonyl complexes
  • Crystal structures
  • Porphyrin complexes
  • Ruthenium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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