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Structural studies of metalloporphyrins. VI — 13 C relaxation time, T 1 , measurements and the nature of the axial N —metal bond in some macrocyclic complexes
Author(s) -
Huet J.,
Gaudemer A.
Publication year - 1981
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/mrc.1270150407
Subject(s) - chemistry , pyridine , rhodium , steric effects , crystallography , cobalt , metal , relaxation (psychology) , bond length , stereochemistry , crystal structure , inorganic chemistry , medicinal chemistry , organic chemistry , catalysis , social psychology , psychology
Rotation barriers around the metal—pyridine bond of various macrocyclic complexes of cobalt(III), rhodium(III), zinc(II) and magnesium(II) have been studied using the 13 C longitudinal relaxation times, T 1 , of the carbon atoms of pyridine and the macrocycle. The data have been rationalized on the basis of steric and electronic factors. The influence of π back‐donation on the rates of rotation around the axial CoN and RhN bonds is discussed. The agreement found between the conclusions drawn from this study and X‐ray data reported for complexes of identical or closely related structure demonstrates the validity of this method.