Molecular environment effects on the reactivity of porphyrins. Influence of basket-handle superstructures on the formation of five-coordinated complexes of iron(II) with neutral nitrogen bases

Journal Article · Wed Oct 29 00:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00282a018· OSTI ID:7032702

Lexa, D; Momenteau, M; Saveant, J M; Xu, F

The association constants of two nitrogen bases, 1,2-dimethylimidazole and 2-methylpyridine, giving rise to five-coordinated iron(II) complexes, have been determined in a series of six iron porphyrins, involving besides tetraphenylporphyrin and orthotetraanisylporphyrin, two ether-linked (C12)/sub 2/ basket-handle porphyrins, protected on one face and on both faces, respectively, and the corresponding two (C12)/sub 2/ secondary amide linked basket-handle porphyrins. Comparison between the unprotected and superstructured complexes shows that the presence of the chains has two effects. One derives from the steric hindrance to axial ligation in porphyrins that are protected on both faces. The other and more remarkable effect is the significant enhancement of the affinity of iron(II) toward the nitrogen base resulting from the presence of the secondary amide groups borne by the chains.

• Research Organization: l'Universite de Paris, France
• OSTI ID: 7032702
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 108:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPLEXES
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
PORPHYRINS
CHEMICAL REACTIONS
BASES
EQUILIBRIUM
EXPERIMENTAL DATA
STEREOCHEMISTRY
CARBOXYLIC ACIDS
COMPLEXES
DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties