Ligand noninnocence in FeNO corroles: insights from β-octabromocorrole complexes

HK Norheim, J Capar, RF Einrem, KJ Gagnon… - Dalton …, 2016 - pubs.rsc.org
Dalton Transactions, 2016pubs.rsc.org
The first FeNO octabromocorroles have been synthesized including four β-octabromo-meso-
tris (pX-phenyl) corrole derivatives Fe [Br8TpXPC](NO)(X= CF3, H, CH3, OCH3) and the β-
octabromo-meso-tris (pentafluorophenyl) corrole complex, Fe [Br8TPFPC](NO). The last
complex, which proved amenable to single-crystal X-ray structure determination, exhibits the
geometry parameters: Fe–N (O) 1.643 (8) Å, N–O 1.158 (9) Å, and a FeNO angle of 176.4
(6)°. The more electron-deficient complexes exhibit increased instability with respect to NO …
The first FeNO octabromocorroles have been synthesized including four β-octabromo-meso-tris(p-X-phenyl)corrole derivatives Fe[Br8TpXPC](NO) (X = CF3, H, CH3, OCH3) and the β-octabromo-meso-tris(pentafluorophenyl)corrole complex, Fe[Br8TPFPC](NO). The last complex, which proved amenable to single-crystal X-ray structure determination, exhibits the geometry parameters: Fe–N(O) 1.643(8) Å, N–O 1.158(9) Å, and a FeNO angle of 176.4(6)°. The more electron-deficient complexes exhibit increased instability with respect to NO loss and also higher infrared NO stretching frequencies (νNO). Interestingly, DFT calculations and IR marker bands indicate a noninnocent {FeNO}7-(corrole˙2−) formulation for all FeNO corroles, both β-H8 and β-Br8, with essentially the same degree of corrole radical character. Instead, an electron-deficient corrole appears to exert a field effect resulting in reduced Fe-to-NO backdonation, which accounts for both the increased instability with respect to NO loss and the higher νNO's.
The Royal Society of Chemistry
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