A ~(13)C and ~1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins

摘要

The crystal structures of chloro(2-aza-2-ethoxycarbonylmethyl-5,10,15,20- tetraphenyl-21-carbaporphyrinato-N,N~′N~(′′)) zinc(ii) [Zn(2-NCH _2COOC _2H _5NCTPP)Cl; 4], (2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N, N~′N~(′′)) palladium(ii) [Pd(2-NCH 2COOC _2H _5NCTPP); 5], bromo(2-aza-2-ethoxycarbonylmethyl-5,10,15, 20-tetraphenyl-21-carbaporphyrinato-N,N~′N~(′′)) manganese(iii) [Mn(2-NCH _2COOC _2H _5NCTPP)Br; 6], [2-aza-(3~′-phenoxypropyl)-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N, N~′N~(′′)] nickel(ii) [Ni(2-NCH _2CH _2CH _2OC _6H _5NCTPP); 7] and chloro(2-aza-2- methoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N, N~′N~(′′)) zinc(ii) [Zn(2-NCH 2COOCH 3NCTPP) Cl; 8] have been established. The g value of 9.54, which was measured from the parallel polarization of the X-band EPR spectra in CHCl _3 at 4 K, is consistent with the high spin mononuclear manganese(iii) centre (S = 2) in 6. The magnitude of the axial (D) zero-field splitting (ZFS) for the mononuclear Mn(iii) centre in 6 was determined approximately to be 1.63 cm ~(-1) by paramagnetic susceptibility measurements. The NMR spectroscopic investigation of the iminium ion with a dipolar canonical contribution to the metal complexes 5-7, Pd(2-NCH _2C _6H _5NCTPP) (10) and Ni(2-NCH _2C _6H _5NCTPP) (11) in CDCl 3 is reported. A resonance between the dipolar canonical form II and covalent canonical form I exists for complexes 5-7, 10 and 11 in CDCl _3. To develop the correlations between δ ~(13)C [C(3)], δ ~1H [H(3)] and the canonical form II in 5-7, 10 and 11, this work thoroughly examines the ~(13)C and ~1H NMR of N ~+CH(Ar) fragment on seven metal complexes of 2-N substituted N-confused porphyrin. According to these results, the ~(13)C [C(3)] and ~1H [H(3)] chemical shifts of the N ~+CH(Ar) fragment at 20 °C in CDCl _3 are separately located at 152.6 ± 0.5 and 8.30 ± 0.15 ppm respectively for the iminium ion. This exists as a dipolar canonical form II for complexes 5-7, 10 and 11, and the N-CH(Ar) group appears at 121.1 ± 0.1 ppm and 6.35 ± 0.01 ppm, which is in a covalent canonical form I contribution to complexes 4 and 8. X-Ray diffraction data indicate that N(2)-C(3) = 1.315 ± 0.011 ? for the dipolar contribution of 5-7, 10-13, while N(2)-C(3) = 1.331 ± 0.008 ? for the covalent contribution of 4 and 8.