Jump to main content
Jump to site search

Issue 2, 1993
Previous Article Next Article

Synthesis, characterization and crystal structures of novel hafnium porphyrins

Abstract

Dichlorohafnium porphyrin complexes [Hf(por)Cl2][por = 2,3,7,8,12,13,17,18-octaethylporphyrinate (oep) or 5,10,15,20-tetraphenylporphyrinate (tpp)] which are potentially useful precursors for various hafnium porphyrin complexes, were synthesised and characterized. The structure of [Hf(oep)Cl2(H2O)] has been determined by X-ray crystallography; the co-ordination geometry around the Hf atom can be described as a 4 : 3 piano-stool with the square base occupied by the porphyrin N atoms and the legs by the two Cl atoms and a water molecule. Treatment of [Hf(por)Cl2] with [NBun4]3[P3O9] gave [NBun4][Hf(por)(P3O9)](por = oep and tpp). The crystal structure of the oep complex revealed a seven-co-ordinate Hf atom surrounded by 4 N atoms of the porphyrin and 3 O atoms of the P3O93– ligand. The N4 and O3 planes are almost parallel and the Hf atom is located 1.007 Å above the N4 plane and 1.476 Å below the O3 plane. Crystal data for [Hf(oep)Cl2(H2O]·C6H6; triclinic, space group P[1 with combining macron], a= 11.977(2), b= 12.261(1), c= 14.677(2)Å, α= 76.74(1), β= 85.41(1), γ= 74.41(1)°, Z= 2; R= 0.081 and R′= 0.092 for 3325 independent reflections with l > 3σ(l). Crystal data for [NBun4][Hf(oep)-(P3O9)]·2CHCl3: monoclinic, space group P21/n, a= 15.490(2), b= 19.133(1), c= 22.761(4)Å, β= 99.425(7)°, Z= 4; R= 0.036 and R′= 0.037 for 4823 independent reflections with l > 3σ(l).

Back to tab navigation

Article type: Paper
DOI: 10.1039/DT9930000205
Citation: J. Chem. Soc., Dalton Trans., 1993,0, 205-209
  •   Request permissions

    Synthesis, characterization and crystal structures of novel hafnium porphyrins

    S. Ryu, D. Whang, J. Kim, W. Yeo and K. Kim, J. Chem. Soc., Dalton Trans., 1993, 0, 205
    DOI: 10.1039/DT9930000205

Search articles by author

Spotlight

Advertisements