Abstract
Single-crystal X-ray structures were obtained for the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F8TPC] and {Fe[F8TPC]}2O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF3 as β-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF3. In other words, Cu[F8TPC] is marginally more saddled than β-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, β-octabromo-meso-triarylcorroles, and β-octaiodo-meso-triarylcorroles, and far less saddled than Cu β-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F8TPC]}2O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe–O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]}2O, where TPFPC3– is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.
Highlights
Well over a half-century ago, the Danish chemist C
Paramagnetic FeCl and Fe−aryl corroles provide some of the most elegant examples of the use of 1H NMR spectroscopy to elucidate the spin density distributions of noninnocent systems.[11−17] These methods, are useless for a considerable number of systems in which intramolecular spin couplings result in a diamagnetic ground state
Key examples of such cryptically noninnocent systems include copper,[18−21] μ-oxodiiron,[11,22] and iron− nitrosyl[23−25] corroles. More indirect means, such as X-ray structure determination and electrochemistry, can be used to glean electronic structure information. It is against this backdrop that we report singlecrystal X-ray structures of the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted Cu[F8TPC] and {Fe[F8TPC]}2O, respectively
Summary
Well over a half-century ago, the Danish chemist C. Paramagnetic FeCl and Fe−aryl corroles provide some of the most elegant examples of the use of 1H NMR spectroscopy to elucidate the spin density distributions of noninnocent systems.[11−17] These methods, are useless for a considerable number of systems in which intramolecular spin couplings result in a diamagnetic ground state. Key examples of such cryptically noninnocent systems include copper,[18−21] μ-oxodiiron,[11,22] and iron− nitrosyl[23−25] corroles. Such studies have been hobbled by an almost[31] complete lack of X-ray crystal structures for β-octafluorocorrole derivatives, a gap in our knowledge that we have been able to close via this study
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