An Octahedral Template Based on a New Molecular Turn: Synthesis and Structure of a Model Complex and a Reactive, Diphenolic Ligand and Its Metal Complexes.
The design and synthesis of a new family of tridentate Schiff base ligands for use in octahedral molecular templates has been successfully demonstrated. As anticipated, two molecules of the ligand, 2,6-pyridinedicarboxaldhydebis(p-hydroxyphenylimine), coordinate equatorially to six-coordinate octahedral metal ions to give orthogonally oriented molecular turns around the anchoring metal ion. This new template offers the advantages that (1) syntheses of the ligand and its complexes are straightforward, giving high yields in simple, one-pot reactions, and (2) structural variations are easily accomplished. X-ray structural analysis has shown that the ligand will only function as a turn when its spatial organization is controlled by coordination to a metal ion. Upon chelation, the phenolic groups are directed across and beyond the metal ion center, and, unlike earlier ligands of this general type which lacked reactive moieties, substitution reactions may be carried out at the free phenolic groups of the octahedral complex. These reactions remain to be optimized in order to achieve the long-term goal of proving their value as synthons for interlocked molecules.
Vance
Andrew L.
AL
Departments of Chemistry, The University of Kansas, Lawrence, Kansas, and University of Warwick, Coventry CV4 7AL, England.
Alcock
Nathaniel W.
NW
Heppert
Joseph A.
JA
Busch
Daryle H.
DH