Binding of Catechols to Iron(III)–Octaethylporphyrin: An Experimental and DFT Investigation

Chaudhary, Arvind; Patra, Ranjan; Rath, Sankar Prasad

doi:10.1002/ejic.201000707

Cited by 33 publications

(23 citation statements)

References 76 publications

(43 reference statements)

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“…A comparison of the 1 H NMR spectra of Pd 2 DEP and Pd 2 DEPR⋅I 3 is shown in Figure (also see Figure S14 in the Supporting Information for a full‐range spectrum of Pd 2 DEPR⋅I 3 ). Trace A shows the well‐resolved spectrum of Pd 2 DEP, in which the two meso ‐proton signals are obseved at 9.72 and 8.32 ppm in 1:2 intensity ratio while the bridging ‐C H 2 and ‐N H signals appear at 5.64 and 6.21 ppm, respectively . However, upon formation of the chlorin–porphyrin heterodimer Pd 2 DEPR⋅I 3 , the 1 H NMR spectrum (trace B) shows a dramatic change.…”

Section: Resultsmentioning

confidence: 99%

Intermacrocyclic Interaction Triggers Facile One‐Pot Synthesis of a Chlorin–Porphyrin Heterodimer

Pandit

Sanfui

Rath

2017

Chemistry A European J

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This work reports a highly facile one-pot synthesis of a new series of fully π-conjugated unsymmetric chlorin-porphyrin heterodimers with quantitative yields by utilizing intermacrocyclic interactions. One-electron oxidations of dicopper(II) and dipalladium(II) porphyrin dimers using mild oxidants such as iodine at room temperature resulted in the formation of a strongly interacting cofacial mixed-valent π-cation radical dimers. The radical, being highly reactive, drives spontaneous and rapid transformation involving a new N=C bond formation, 1,2-ethyl migration, and the generation of a new indolizinium ring that bridges between the two macrocycles. X-ray structural characterization of the heterodimers reveals that the two macrocycles are nearly coplanar and thereby extends the π-conjugation from one end to the other. DFT calculations that reproduce the experimental results are also reported.

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Section: Resultsmentioning

confidence: 99%

Intermacrocyclic Interaction Triggers Facile One‐Pot Synthesis of a Chlorin–Porphyrin Heterodimer

Pandit

Sanfui

Rath

2017

Chemistry A European J

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“…For the function and structure of catalase, see: Nicholls et al (2001). For the structures of other related ferric pheno porphyrin derivatives, see: Chaudhary et al (2010); Ueyama et al (1998); Kanamori et al (2005). For the typical geometry parameters for high-spin ferric porphyrin complexes, see: Scheidt & Reed (1981).…”

Section: Related Literaturementioning

confidence: 99%

“…Heme catalase contains an active-site tyrosine, a phenolato type ligand, that binds to the heme iron center (Nicholls et al, 2001). A number of iron phenolate porphyrin complexes has been prepared and structurally characterized (Chaudhary et al, 2010, Ueyama et al, 1998, Kanamori et al, 2005. In this paper, we report the structure of (5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato)(tetrafluorophenolato)iron(III) with a cyclohexane monosolvate.…”

Section: S1 Commentmentioning

confidence: 99%

(2,3,5,6-Tetrafluorophenolato)[5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]iron(III) cyclohexane monosolvate

Powell

Richter‐Addo

2013

Acta Cryst E

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The title compound, [Fe(C6HF4O)(C48H36N4O4)]·C6H12, represents a five-coordinate iron(III) porphyrin complex in a square-pyramidal geometry with a tetrafluorophenolate anion as the axial ligand. The FeIII atom is displaced by 0.364 (2) Å from the 24-atom mean plane of the porphyrinate ring towards the tetrafluoro phenolate anion. The average Fe—N distance is 2.053 (2) Å and the Fe—O distance is 1.883 (2) Å. A porphyrin aryl H atom points in the general direction of the phenoxide ring. The mean plane separation between the 24-atom porphyrin planes of two adjacent porphyrin rings is ∼3.7 Å, and the lateral shift is ∼3.5 Å resu, ting in an Fe⋯Fe separation of 5.6167 (14) Å.

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“…Similar observations are also reported when thiolates and catecholates are used as axial ligands. 12,23 Figure 8A demonstrates the Mulliken spin densities using DFT of the phenolato carbons for 2a in which spin densities observed positive at ortho and para posi- tions, while negative at meta positions. As a result, the ortho-and para-protons would be shifted upfield while meta-protons in the downfield region as also observed in the 1 H NMR of the molecule.…”

Section: H Nmrmentioning

confidence: 99%

“…10 However, phenolato binding to Fe(III)porphyrins are known for quite some time which forms five-coordinate complex where phenols bind in a η 1 -binding mode. 11,12 Trans-1,2-bis(meso-octaethylporphyrinyl)ethene are used in the present investigations in which two por-phyrin macrocycles are placed in the trans position of an ethene linker leading to strong electronic communications between them in a single molecular framework.…”

Section: Introductionmentioning

confidence: 99%

Axial phenoxide coordination on di-iron(III) bisporphyrin: Insights from experimental and DFT studies

et al. 2011

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Synthesis, structure and properties of new five-coordinate phenolate complexes of di-iron(III) bisporphyrin are reported here, in which phenol binds in η 1-fashion as an axial ligand. The solid and solution EPR at 120 K and 1 H NMR spectral pattern in solution provide unequivocal evidence for the high spin (S = 5/2) nature of the complex. Mulliken spin density calculation using DFT demonstrates the positive spin densities at the meso carbons and negative spin densities at the methylene carbons and, as a result, the meso and methylene protons are shifted in the upfield and down field regions, respectively in the 1 H NMR spectra of the molecule. Also, the ortho-and para-protons of the phenolate ligands are observed to be shifted in the upfield region while meta-protons are shifted downfield. The alternating shift pattern, which is the opposite sign of the chemical shifts for meta-versus ortho-and para-protons, was also explained due to negative and positive spin densities, respectively on the carbons and indicative of π spin delocalization on the phenolate ligand. Thus, the calculated spin density maps accounted for the essential 1 H NMR spectroscopic features that are observed here for the phenolate complexes of di-iron(III) bisporphyrin. The temperature dependence of the signals follows the Curie law which is indicative of single spin state throughout the temperature range of −40 to +40 • C. The single crystal X-ray structure of the corresponding chloro derivative, trans 1,2-bis(chloroiron(III) octaethyl porphyrinyl)ethene, has also been reported here which authenticates the high-spin nature of the complex.

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Binding of Catechols to Iron(III)–Octaethylporphyrin: An Experimental and DFT Investigation

Cited by 33 publications

References 76 publications

Intermacrocyclic Interaction Triggers Facile One‐Pot Synthesis of a Chlorin–Porphyrin Heterodimer

Intermacrocyclic Interaction Triggers Facile One‐Pot Synthesis of a Chlorin–Porphyrin Heterodimer

(2,3,5,6-Tetrafluorophenolato)[5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]iron(III) cyclohexane monosolvate

Axial phenoxide coordination on di-iron(III) bisporphyrin: Insights from experimental and DFT studies

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