Metal complexes of 2-aza-2-benzyloxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrin: M(2-NCH₂COOCH₂C₆H₅NCTPP) (M = Ni²⁺, Pd²⁺) and Mn(2-NCH₂COOCH₂C₆H₅NCTPP)Br (NCTPP = N-confused 5,10,15,20-tetraphenylporphyrinat

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• 作者：Yu-Cheng Wang ; Jyh-Horung Chen ; Shin-Shin Wang ; Jo-Yu Tung
• 关键词：X-ray diffraction ; Nickel(II) N-confused porphyrin ; Palladium(II) N-confused porphyrin ; Manganese(III) N-confused porphyrin ; Dipolar canonical form
• 刊名：Polyhedron
• 出版年：28 January, 2014
• 年：2014
• 卷：68
• 期：Complete
• 页码：23-31
• 全文大小：1063 K

文摘

The crystal structures of (2-aza-2-benzyloxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N鈥?N鈥?nickel(II) [Ni(2-NCH₂COOCH₂C₆H₅NCTPP); 5], (2-aza-2-benzyloxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N鈥?N鈥?palladium(II) toluene solvate [Pd(2-NCH₂COOCH₂C₆H₅NCTPP)路C₆H₅CH₃; 6路C₆H₅CH₃] and bromo(2-aza-2-benzyloxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N鈥?N鈥?manganese(III) ethyl acetate solvate [Mn(2-NCH₂COOCH₂C₆H₅NCTPP)Br路EtOAc; 7路EtOAc] have been established. The coordination sphere around the Ni²⁺ ion in 5 (or Pd²⁺ ion in 6路C₆H₅CH₃) is distorted square planar (DSP), whereas for Mn³⁺ in 7路EtOAc, it is square-based pyramidal with the Br atom lying in the axial site. The g value of 10.98 measured from the parallel polarization of the X-band ESR spectrum at 4 K is consistent with a high spin mononuclear manganese(III) centre (S = 2) in 7. The magnitude of the axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) centre in 7 was determined to be approximately 0.52 cm^鈭? by paramagnetic susceptibility measurements. The ¹³C [C(19)] and ¹H [H(19)] chemical shifts of the N⁺CH(Ar) fragment at 20 掳C in CDCl₃ are located at 未 152.5 卤 0.5 and 8.21 卤 0.04 ppm respectively for the iminium ion of the dipolar form in complexes 5-7. From the X-ray diffraction data, the N(4)-C(19) bond length of 1.312 卤 0.013 脜 indicates the existence of the dipolar form for 5-7.