The NMR spectra of the porphyrins. 17—Metalloporphyrins as diamagnetic shift reagents, structural and specificity studies
作者:
Raymond J. Abraham,
Geoffrey R. Bedford,
Brian Wright,
期刊:
Organic Magnetic Resonance
(WILEY Available online 1982)
卷期:
Volume 18,
issue 1
页码: 45-52
ISSN:0030-4921
年代: 1982
DOI:10.1002/mrc.1270180111
出版商: John Wiley&Sons Limited
数据来源: WILEY
摘要:
AbstractThe nature of the metalloporphyrin‐ligand complexes produced by zinc, magnesium and cobalt porphyrins with basic ligands has been investigated using the diamagnetic ring current shifts of the porphyrin on the ligand protons. The metal to nitrogen bond lengths in some metallo‐meso‐tetraphenylporphyrin (pyridine) complexes have been determined and compared with the data of the crystalline complexes. The geometry of the Znmeso‐tetraphenylporphyrin complexes with 2‐picoline, quinoline and isoquinoline has been investigated. Steric interactions between the ligand and the porphyrin in 2‐picoline and quinoline produce a dramatic increase in the ZnN bond length when compared to the unstrained analogues pyridine and isoquinoline. This large increase is associated with comparatively minor angle distortions in the complex. The specificity of the Znmeso‐tetraphenylporphyrin complexation shifts has been determined for a range of benzyl and butyl compounds. The complexation shift is linearly related to the basicity of the ligand for a wide rang
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