Metal complexes of tetradentate and pentadentate N-o-hydroxybenzamido-meso-tetraphenylporphyrin ligand: M(N-NCO(o-OH)C6H4-tpp) (M = Zn2+, Ni2+, Cu2+) and M '(N-NCO(o-O) C6H4-tpp) (M '= Mn3+) (tpp=5, 10, 15, 20-tetraphenylporphyrinate)

摘要

The crystal structures of N-o-hydroxybenzimido-meso-tetraphenylporphyrinatozinc(II) toluene solvate [Zn(N-NCO(o-OH)C6H4-tpp)center dot C6H5CH3; 4 center dot C6H5CH3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatonickel(II) chloroform solvate [Ni(N-NCO(o-OH)C6H4-tpp)center dot 0.6CHCl(3); 5 center dot 0.6 CHCl3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatocopper(II) toluene solvate [Cu(N-NCO(o-OH)C6H4-tpp)center dot C6H5CH3; 6.C6H5CH3] and N-o-oxido-benzimido-meso-tetraphenylporphyrinato(-kappa(4),N-1,N-2,N-3,N -5,kappa O-2) manganese (III) methylene chloride. methanol solvate [Mn(N-NCO(o-O)C6H4-tpp)center dot CH2Cl2 center dot MeOH; 8 center dot CH2Cl2 center dot MeOH] were established. The coordination sphere around Zn2+ ion in 4 center dot C6H5CH3, (or Ni2+ ion in 5-0.6 CHCl3 or Cu2+ ion in 6 center dot C6H5CH3) is a distorted square planar (DSP) whereas for Mn3+ in 8 center dot CH2Cl2 center dot MeOH, it is a distorted trigonal bipyramid (DTBP) with O(1). N(1) and N(3) lying in the equatorial plane for 8 center dot CH2Cl2 center dot MeOH. The g value of 8.27 measured from the parallel polarization of X-band EPR spectra at 293 K is consistent with the high-spin mononuclear manganese(III) (S = 2) in 8. The magnitude of axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) in 8 was determined approximately as 3.0 cm(-1) by the paramagnetic susceptibility measurements and conventional EPR spectroscopy.