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A Dynamic Tricopper Double Helicate
Author(s) -
Hutin Marie,
Frantz Richard,
Nitschke Jonathan R.
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600079
Subject(s) - aniline , imine , covalent bond , chemistry , tetrafluoroborate , copper , yield (engineering) , polymer chemistry , phenanthroline , stereochemistry , combinatorial chemistry , crystallography , materials science , organic chemistry , metallurgy , catalysis , ionic liquid
The reaction between 8‐aminoquinoline, 1,10‐phenantholine‐2,9‐dicarbaldehyde, and copper( I ) tetrafluoroborate gave a quantitative yield of a tricopper double helicate. The presence of dynamic covalent imine (CN) bonds allowed this assembly to participate in two reactions not previously known in helicate chemistry: 1) It could be prepared through subcomponent substitution from a dicopper double helicate that contained aniline residues. An electron‐poor aniline was quantitatively displaced; a more electron‐rich aniline competed effectively with the aminoquinoline, setting up an equilibrium between dicopper and tricopper helicates that could be displaced towards the tricopper through the addition of further copper( I ). 2) Both dicopper and tricopper helicates could be prepared simultaneously from a mixture of phenanthroline dialdehyde, aniline, and aminoquinoline, which contained all possible imine condensation products in equilibrium. Following the addition of copper( I ), thermodynamic equilibration on both covalent and coordinative levels eliminated all partially‐formed and mixed imine ligands from the mixture, leaving the helicates as exclusive products.