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Structure and Chemistry of N ‐Substituted Corroles and Their Rhodium( I ) and Zinc( II ) Metal‐Ion Complexes
Author(s) -
Simkhovich Liliya,
Iyer Parameswar,
Goldberg Israel,
Gross Zeev
Publication year - 2002
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(20020603)8:11<2595::aid-chem2595>3.0.co;2-a
Subject(s) - rhodium , zinc , chemistry , metal , ion , metal ions in aqueous solution , inorganic chemistry , organic chemistry , catalysis
In the present work we report on the detailed structural features of the chiral N 21 ‐ and N 22 ‐substituted benzyl and picolyl derivatives of tris(pentafluorophenyl)corrole [H 3 (tpfc)]. The main difference between the isomers is that substitution on N 22 creates a much more crowded environment, reflected in higher deformation of the corrole ring from planarity and of the meso ‐aryls from perpendicular orientation. The effects of metal‐ion chelation on corrole geometry are demonstrated by structural investigations of the zinc( II ) and rhodium( I ) complexes of the N 21 ‐ and N 22 ‐alkylated corroles. The major finding is the intramolecular coordination of the pyridine moiety of the picolyl substituent in the case of [Zn II ( N 21 ‐picolyl‐tpfc)]. This pyridine is readily attracted to the zinc ion as an axial ligand, thus replacing the external pyridine molecule of the precursor [Zn II ( N 21 ‐benzyl‐tpfc)(py)]. The change is associated with a considerable flattening of the corrole ring in order to allow a more convenient coordination of the zinc ion to all four pyrrole nitrogen atoms (at Zn–N(pyrrole) distances of 1.956–1.987 Å for the nonsubstituted sites, and 2.224–2.247 Å for the substituted sites). These structural investigations also aid a good understanding of the spectroscopic characteristics of the derivatives.