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Metal Complexes of a Biconcave Porphyrin with D 4 ‐Structure—Versatile Chiral Shift Agents
Author(s) -
Schwenninger Reinhold,
Schlögl Johann,
Maynollo Josef,
Gruber Karl,
Ochsenbein Philippe,
Bürgi HansBeat,
Konrat Robert,
Kräutler Bernhard
Publication year - 2001
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 - 10.1002/1521-3765(20010618)7:12<2676::aid-chem26760>3.0.co;2-i
Subject(s) - porphyrin , chemistry , metal , enantiomer , fullerene , ligand (biochemistry) , crystallography , stereochemistry , polymer chemistry , photochemistry , organic chemistry , biochemistry , receptor
Representative metal complexes of a biconcave D 4 ‐symmetric porphyrin were synthesised by metal‐ion insertion into the porphyrin ligand 1 . The NMR spectra suggested D 4 ‐symmetry for the Zn II and dioxo‐Ru VI complexes of 1 and C 4 ‐symmetry for the unsymmetrically ligated Ru II and Rh III complexes. Metal complexes of 1 proved to be versatile chiral 1 H NMR shift agents for a broad spectrum of organic amines, alcohols, carboxylic acids, esters, nitriles and nonpolar fullerene derivatives. A practical analysis of chiral substrates with 1 covers enantiomeric excesses beyond 99 %. An X‐ray structure of (1:1)‐cocrystals of an achiral, biconcave Co II porphyrinate and C 60 provided the first detailed insights into the structure of such a biconcave metallo–porphyrinate. It also showed remarkable packing of the carbon sphere against the main concave units of the porphyrin and gave clues about the relevant interactions between biconcave porphyrins and fullerenes.