Structural consequences of deacylation of nickel(II) cyclidenes in acidic and basic conditions

Two nickel(II) complexes with deacylated unsaturated tetraaza macrocyclic cyclidene ligands were isolated and structurally characterized. Under acidic conditions, both acyl groups attached to the gamma carbons in the precursor complex are cleaved off, yielding a symmetric dicationic complex (IIIc) w...

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Bibliographic Details
Published inJournal of inclusion phenomena and macrocyclic chemistry Vol. 42; no. 1-2; pp. 83 - 87
Main Authors Nazarenko, AY, Robinson, PD, Wilson, RM, Kolchinski, AG, Disch, JS, Rybak-Akimova, EV
Format Journal Article
LanguageEnglish
Published DORDRECHT Springer Nature 01.02.2002
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
LACUNAR
COMPLEXES
crystal structure
macrocyclic complexes
DIOXYGEN ADDUCTS
IRON
molecular shape
nickel complexes
BINDING
MOLECULAR-MECHANICS
COBALT
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Summary:Two nickel(II) complexes with deacylated unsaturated tetraaza macrocyclic cyclidene ligands were isolated and structurally characterized. Under acidic conditions, both acyl groups attached to the gamma carbons in the precursor complex are cleaved off, yielding a symmetric dicationic complex (IIIc) which retains the usual saddle shaped conformation of the 16-membered cyclidene complexes. Under basic conditions, one acyl group remains attached to the cyclidene, while the other (deacylated) chelate ring becomes singly deprotonated. This asymmetric deacylation is observed for the first time in the family of cisdimethyl cyclidenes. The presence of a deprotonated conjugated chelate ring in the 15-membered macrocycle (VIb) results in the overall planar shape of the molecule.
ISSN:1388-3127
1573-1111
DOI:10.1023/A:1014543911596