Chlorido(pyridine-κN)(5,10,15,20-tetraphenylporphyrinato-κ4N)cobalt(III) chloroform hemisolvate

Belghith, Yassin; Daran, Jean‐Claude; Nasri, Habib

doi:10.1107/s1600536812032564

Cited by 7 publications

(4 citation statements)

References 18 publications

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“…Cobalt K-edge XAS data were obtained for Co[TPC](PPh 3 ) and compared with those of the presumptive bona fide Co(III) complexes Co[TPC](py) 2 and Co[TPP](py)Cl (TPP = tetraphenylporphyrin, Figure ). The metal K-edge (rising edge) energy position is generally a good indicator of the charge on the absorbing metal ion …”

Section: Resultsmentioning

confidence: 99%

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

et al. 2017

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A reinvestigation of cobalt-corrole-triphenylphosphine complexes has yielded an unexpectedly subtle picture of their electronic structures. UV-vis absorption spectroscopy, skeletal bond length alternations observed in X-ray structures, and broken-symmetry DFT (B3LYP) calculations suggest partial Co-corrole character for these complexes. The same probes applied to the analogous rhodium corroles evince no evidence of a noninnocent corrole. X-ray absorption spectroscopic studies showed that the Co K rising edge of Co[TPC](PPh) (TPC = triphenylcorrole) is red-shifted by ∼1.8 eV relative to the bona fide Co(III) complexes Co[TPC](py) and Co[TPP](py)Cl (TPP = tetraphenylporphyrin, py = pyridine), consistent with a partial Co-corrole description for Co[TPC](PPh). Electrochemical measurements have shown that both the Co and Rh complexes undergo two reversible oxidations and one to two irreversible reductions. In particular, the first reduction of the Rh corroles occurs at significantly more negative potentials than that of the Co corroles, reflecting significantly higher stability of the Rh(III) state relative to Co(III). Together, the results presented herein suggest that cobalt-corrole-triphenylphosphine complexes are significantly noninnocent with moderate Co-corrole character, underscoring-yet again-the ubiquity of ligand noninnocence among first-row transition metal corroles.

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Section: Resultsmentioning

confidence: 99%

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

et al. 2017

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“…[26][27][28][29][30] However, most of the porphyrin complexes with Co III central metal were reported to be largely deformed in ruffled forms. [31][32][33] It should be noted that this trend, smaller central metal leads to larger deformation of the pophyrinato ligand, is a rough view. The central metal size may be only one of the factors that deform the porphyrinato ligand, and some (porphyrinato)cobalt complexes do not follow this tendency probably due to the packing forces.…”

Section: Somo Of Co(tmp)(cn) 2 Neutral Radicalmentioning

confidence: 99%

Structural and transport properties of neutral radical crystals of Co^III(tmp)(CN)₂(tmp = 5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co^III(tmp)(CN)]_n

et al. 2017

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An axially ligated Co(tmp) (tmp = 5,10,15,20-tetramethylporphyrinato) anion, [Co(tmp)(CN)], has been prepared and subjected to electrochemical oxidation to obtain the open shell tmp π-ligand. With acetone as the solvent, solvent-free neutral radical crystals of Co(tmp)(CN) are obtained, whereas solvent-inclusive crystals of Co(tmp)(CN)·2CHCN are obtained with CHCN as the solvent. In both crystals, the open shell tmp ring deforms into a ruffled form, which makes the π-π interactions in the crystal weak. Thus, the electrical conductivity is low, and the crystals behave as semiconductors with a room temperature resistivity of 10 Ω cm and an activation energy of about 0.3 eV. When the solvent is acetone, non-oxidized crystals of the CN-bridged polymer {[Co(tmp)(CN)](acetone)} are obtained as a byproduct. The closed shell tmp ring deforms into a ruffled form, and there π-π interactions in the crystal are negligible. The room temperature resistivity is rather high at about 10 Ω cm.

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“…For general background to magnesium porphyrin species and their applications, see: Ghosh et al (2010). For related structures, see: Belghith et al (2012); McArdle (1995); McKee et al (1984); Choon et al (1986); McKee & Rodley (1988); Gryz et al (2007); Imaz et al (2005). For a description of the Cambridge Structural Database, see: Allen (2002).…”

Section: Related Literaturementioning

confidence: 99%

Diaqua(5,10,15,20-tetraphenylporphyrinato-κ⁴N)magnesium–18-crown-6 (1/1)

Ezzayani¹,

Nasri²,

Belkhiria³

et al. 2013

Acta Cryst E

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In the title compound, [Mg(C44H28N4)(H2O)2]·C12H24O6, the MgII cation lies on an inversion center and is octahedrally coordinated by the four N atoms of the deprotonated tetraphenylporphyrin (TPP) ligand and by two water molecules. The asymmetric unit contains one half of the [Mg(TPP)(H2O)2] complex and one half of an 18-crown-6 molecule. The average equatorial magnesium–pyrrole N atom distance (Mg—Np) is 2.071 (1) Å and the axial Mg—O(H2O) bond length is 2.213 (1) Å. The crystal packing is stabilized by two O—H⋯O hydrogen bonds between coordinating water molecules and adjacent 18-crown-6 molecules, and exhibits a one-dimensional supramolecular structure along the a axis. The supramolecular architecture is futher stabilized by weak C—H⋯π interactions. The 18-crown-6 molecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.

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Chlorido(pyridine-κN)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)cobalt(III) chloroform hemisolvate

Cited by 7 publications

References 18 publications

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

Structural and transport properties of neutral radical crystals of Co^III(tmp)(CN)₂(tmp = 5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co^III(tmp)(CN)]_n

Diaqua(5,10,15,20-tetraphenylporphyrinato-κ⁴N)magnesium–18-crown-6 (1/1)

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Chlorido(pyridine-κN)(5,10,15,20-tetraphenylporphyrinato-κ4N)cobalt(III) chloroform hemisolvate

Cited by 7 publications

References 18 publications

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

Structural and transport properties of neutral radical crystals of CoIII(tmp)(CN)2(tmp = 5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [CoIII(tmp)(CN)]n

Diaqua(5,10,15,20-tetraphenylporphyrinato-κ4N)magnesium–18-crown-6 (1/1)

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Chlorido(pyridine-κN)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)cobalt(III) chloroform hemisolvate

Structural and transport properties of neutral radical crystals of Co^III(tmp)(CN)₂(tmp = 5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co^III(tmp)(CN)]_n

Diaqua(5,10,15,20-tetraphenylporphyrinato-κ⁴N)magnesium–18-crown-6 (1/1)