四-(邻氯苯基)卟吩及其金属络合物的核磁共振谱

在四-(邻氯苯基)卟吩及其金属络合物中,苯环上一个邻位质子被氯原子取代,导致其余苯环质子和全部苯环碳原子成为磁不等性核,从而出现比未取代的四苯基卟吩及其金属络合物为多的化学位移。对于In(OClTPP)Cl,NMR时标上缓慢的轴向配位体交换和苯环相对于卟啉平面的缓慢旋转,导致苯环两侧的不等性;因此,苯环邻位和间位的质子和碳原子各呈现两个不同的化学位移值。本工作测量和归属了H_2(OClTPP)及其诈、镉、镍、铟络合物的质子谱和~(13)C谱,使用偏共振实验以辅助谱的归属。

NMR SPECTRA OF TETRAKIS(ORTHO-CHLOROPHENYL)PORPHIN AND ITS METAL-COMPLEXES

In tetrakis(ortho-chlorophenyl)porphin and its metal-complexes,the un-symmetric replacement of a single ortho-phenyl proton by a chlorine atom in each phenylring causes magnetic nonequivalence of the remaining phenyl protons and all phenyl car-bon atoms,giving rise to additional chemical shifts as compared to the original tetra-phenylporphin and its metal-complexes.In the case of In(OCITPP)Cl,slow axial ligandexchange and slow rotation of the phenyl ring(on the NMR time scale)with respect tothe plane of the porphyrin causes nonequivalence of the two sides of each phenyl ring:therefore,protons and carbon atoms on the ortho-and meta-phenyl positions display dif-ferent chemical shift values.The proton and ~13C NMR Spectra of H_2(OCITPP)and theZn,Cd,Ni and In complexes were obtained and assigned.Off-resonance experiments wereused to facilitate the assignment.