Phenyl Derivative of Iron 5,10,15-Tritolylcorrole

Nardis, Sara; Cicero, Daniel O.; Licoccia, Silvia; Pomarico, Giuseppe; Berna, Beatrice Berionni; Sette, Marco; Ricciardi, Giampaolo; Rosa, Angela; Fronczek, Frank R.; Smith, Kevin M.; Paolesse, Roberto

doi:10.1021/ic5003572

Cited by 28 publications

(25 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In a first approximation, no substantial spin populations were found to reside on the corrole ligand . The 1 H NMR spectra (Table ) also evince no indication of an “a 2u ‐type” corrole radical, which would have led to significant paramagnetic shifts for meso ‐aryl protons . Careful examination of the DFT spin density profile does, however, reveal small excess spin populations at certain carbon atoms, including the β ‐carbons C 3/17 and C 8/12 and the ortho and para carbons of the axial phenyl group.…”

Section: Resultsmentioning

confidence: 88%

“…[1,5,23] The 1 HNMR spectra (Table 2) also evince no indication of an "a 2u -type"c orrole radical, which would have led to significant paramagnetic shifts for meso-aryl protons. [24] Carefule xamination of the DFT spin density profile does, however,r eveal small excess spin populations at certain carbon atoms, including the b-carbons C 3/17 and C 8/12 and the ortho and para carbons of the axial phenyl group. These also happent ob et he positions at whicht he attached protons exhibit the largest paramagnetic shifts (Table2), which strongly suggestst hat the DFT spin density profile provides ar elatively accurate representation of reality.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Ligand Noninnocence in Iron Corroles: Insights from Optical and X‐ray Absorption Spectroscopies and Electrochemical Redox Potentials

Ganguly

Giles

Thomas

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

Two new series of iron meso-tris(para-X-phenyl)-corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]}2O, and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected FeIV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be FeIII-like. These results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.

show abstract

Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Ligand Noninnocence in Iron Corroles: Insights from Optical and X‐ray Absorption Spectroscopies and Electrochemical Redox Potentials

Ganguly

Giles

Thomas

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Moreover, the NMR features of 6 in benzene-d 6 are similar to those of other Fe(IV) triphenylcorrole complexes containing carbonbased ligands. 3,31 Unfortunately, compound 6 proved to be challenging to isolate in bulk due to its spontaneous decomposition to 2•L after several hours in solution. However, we were able to obtain single crystals that were suitable for Xray diffraction.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Iron(II) Corrole Anions

et al. 2019

View full text Add to dashboard Cite

Reduction of [Fe(TPC)(THF)] (TPC = trianion of 5,10,15-triphenylcorrole) with KC8 generates the iron(II) corrole anion, K(THF)2[FeII(TPC)] (3a). Compound 3a represents the first example of an isolated and crystallographically characterized corrole complex of divalent iron. The compound adopts an intermediate-spin state (S = 1), displaying square-planar geometry about the iron atom. All-electron density functional theory (OLYP and B3LYP) calculations with STO-TZP basis sets indicate two essentially equienergetic d electron configurations, d xy 2d z 2 2d xz 1d yz 1 (occupation 1) and d xy 2d z 2 1d xz 1d yz 2 (occupation 2), as likely contenders for the ground state of [FeII(TPC)]−, with the optimized geometry of the former in slightly better agreement with the low-temperature X-ray structure. Solutions of 3a react with carbon monoxide to afford the low-spin (S = 0) complex, [Fe(TPC)(CO)]−, whereas introduction of oxygen at −78 °C leads to a putative O2 adduct, [Fe(TPC)(O2)]−, which decays rapidly even at low temperatures. Treatment of 3a with organic electrophiles results in formal oxidative addition to give both iron(III) and iron(IV) corrole species. With iodomethane, [Fe(TPC)Me] is produced, illustrating the first instance of alkyl ligand coordination in an iron corrole complex.

show abstract

“…[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Corrole has excellent chelating properties; many metal complexes across the periodic table bearing corrole ligand functionalities have already been reported in the literature. [50][51][52][53][54][55][56][57][58][59][60][61][62][63] Licoccia et al first synthesized oxo(corrolato)vanadium(IV) complexes bearing b-substitution at the corrole periphery. 64 Interestingly, to date, there is no report on the oxo(corrolato)vanadium(IV) complexes bearing meso-substitution at the corrole periphery.…”

Section: Introductionmentioning

confidence: 99%