Control of the Helical Chirality in Octahedral Complexes by a Chiral Macrobicyclic Cavity Possessing Six Convergent Hydroxyl Groups

Abstract

The (aR,aR,uR) and (uS,aS,aS) enantiomers of a chiral macrobicyclic ligand with a bicapped tris(binaphtho1) structure were synthesized. Complexation of galliKeywords um(III), chromium(ni) and iron(1n) centres in the chiral cavities of these two ligands chirality * coordination modesyielded exclusively one octahedral configuration in each case: the (aR,aR,aR) enanmacrocyclic ligands -octahedral comtiomer gave a A complex and the (uS,aS,aS) enantiomer a A complex. These assignplexes * supramolecular chemistry ments were established by CD spectroscopy for chromium and iron centres and by molecular modelling.

Syntheses, Crystal Structures, and CD Spectra of Simple Heterobimetallic Transition Metal Binaphtholates

“…1 The complexes provide convenient models for a set of Fe(III) and Cr(III) macrobicyclic ligand complexes recently reported. 24…”

“…A brief account of an Al analogue has been published, and the preparation of W VI (binaphtholate) 3 has been reported 17 but no crystal structure was obtained. The nearest analogues of our complexes are the tris(catecholate) complexes of Fe(III) and Cr(III) prepared by Raymond et al There is a recent report of the Ga(III), Fe(III), and Cr(III) complexes of a macrobicyclic ligand based on binaphthol, but again no crystal structures are reported. We describe here the isolation, crystal structures, and CD and absorption spectra of the heterobimetallic complexes Na 3 [Fe( S -binaphtholate) 3 ]·3Et 2 O·H 2 O, Li 3 [Fe( R -binaphtholate) 3 ]·6THF, and Li 3 [Cr( R -binaphtholate) 3 ]·6THF.…”

“…ReV. 23 There is a recent report 24 of the Ga(III), Fe(III), and Cr(III) complexes of a macrobicyclic ligand based on binaphthol, but again no crystal structures are reported. We describe here the isolation, crystal structures, and CD and absorption spectra of the heterobimetallic complexes Na 3 [Fe(S-binaphtholate…”

Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

“…All commercially available compounds were purchased from commercial sources and used as received. Racemic or ( R )- 2 [ 40 – 41 ], racemic or ( R )- 3 [ 42 ], 4c [ 43 ], 4d [ 44 ] and ( R )- 7 [ 45 ] were prepared according to literature procedures. THF (Na), CH 2 Cl 2 (CaH 2 ) and CHCl 3 (4 Å molecular sieves) were dried before use.…”

Tailored synthesis of branched polymers with poly(tetrahydrofuran) having an azetidinium salt end group

“…1-(Diphenylmethyl)azetidine (Aldrich; 98%) was used as received. 2,29-Dihydroxy-1,19-binaphthyl-3,39-dicarboxylic acid was prepared by a copper-catalyzed oxidative coupling reaction 19) of methyl 2-hydroxy-3-naphthoate, and subsequent hydrolysis under alkaline condition 20) . Sodium benzoate (2 a), sodium terephthalate (2c) and sodium tartarate (2i) were used as received.…”