Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and a gold undecaarylcorrole

Capar, Jan; Zonneveld, Job; Berg, Steffen; Isaksson, Johan; Gagnon, Kevin J.; Thomas, Kolle E.; Ghosh, Abhik

doi:10.1016/j.jinorgbio.2016.06.026

Cited by 19 publications

(21 citation statements)

References 35 publications

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“…After stirring for 1h,t he purple suspension obtained was washed twice with distilled water and once with saturated aqueous NaHCO 3 .T he orange CH 2 Cl 2 phase was dried over Na 2 SO 4 ,f iltered, evaporated to am inimum volume, and chromatographed on as ilica gel column. Elution with 1:1 n-hexane/CH 2 Cl 2 led to ab rown band identified with HR-ESI as the detrifluoromethylated product H 3 [(CF 3 ) 7 TpMeOPC] (1.2 mg), whereas 2:3 n-hexane/ CH 2 Cl 2 resulted in H 3 [5-OH,10-H-(CF 3 ) 8 TpOMePC] as an orange band (25 mg, 88 %). UV/Vis (CH 2 Cl 2 ): l max ,n m( e 10 À4 ,M À1 cm À1 ): 486 (2.57).…”

Section: Synthesis Of Co II [Iso-10-oh-br 8 Tpc](pph 3 )mentioning

confidence: 99%

“…Details of such ap rotocol have recently been published for undecaarylisocorroles. [7] Presented herein are the results of our continued studies on sterically hindered isocorroles, including optimized protocols for the synthesis of 5/10hydroxy-b-octabromo-meso-triphenylisocorrole, H 2 [iso-5/10-OH-Br 8 TPC],a nd its complexation to Co II and Ni II .A lso presented are our first resultso nt he demetalation of ac opper b-octakis-(trifluoromethyl)-meso-triarylcorrole. The various products obtained were characterized as far as possible with single-crystal X-ray crystallography;a sd iscussed below,t he results, at otal of five X-ray structures (Table 1), provide substantial insights into the structural characteristics of isocorrole derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…We also discovered that prolonged exposure to an acidic medium such as CHCl 3 /H 2 SO 4 without an added reductant resulted in moderate yields of 5‐ and 10‐hydroxyisocorroles. Details of such a protocol have recently been published for undecaarylisocorroles . Presented herein are the results of our continued studies on sterically hindered isocorroles, including optimized protocols for the synthesis of 5/10‐hydroxy‐β‐octabromo‐ meso ‐triphenylisocorrole, H 2 [ iso ‐5/10‐OH‐Br 8 TPC], and its complexation to Co II and Ni II .…”

Section: Introductionmentioning

confidence: 99%

“…Single-crystal Xray structures were obtained for H 2 [iso-5-OH-Br 8 TPC] (Figure 3), Co II [iso-10-OH-Br 8 TPC](PPh 3 )( Figure 4), and Ni II [iso-5-OH-Br 8 TPC] ( Figure 5). The structures exhibit short metal-nitrogen distan- (5)13.8275 (7) 14.5129 (6) 13.3041 (7) 25.9102 (7) ces and essentially planar isocorrole cores. Like corroles, isocorroles thus appear to be strongly resistant to nonplanar distor-tions, which is thought to be ac onsequence of the rigidity of the C1-C19 pyrrole-pyrrole linkagea nd its resistance to both twistinga nd pyramidalization.B oth metalloisocorrole structures exhibit intramolecular hydrogen bonding involving the meso-OH groups and intermolecular metal-b-bromine interactions ( Figure 4a nd Figure 5).…”

Section: Introductionmentioning

confidence: 99%

“…X-ray structure of Co II [iso-10-OH-Br 8 TPC](PPh 3 ): a) top view,b)side-view showing 10-OH···p(PPh 3 )h ydrogen bonding, and c) side view showing stacking and Co···Br interactions (). Selectedd istances:Co(1)-N(1) 1.887(2), Co(1)-N(2) 1.930(2), Co(1)-N(3) 1.927(2), Co(1)-N(4)1 .881(2), and Co(1)-P(1) 2.3837(7) .ChemistryOpen 2017, 6,402 -409 www.chemistryopen.org 2017 The Authors. Publishedb yWiley-VCH Verlag GmbH &Co. KGaA, Weinheim…”

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β‐Octabromo‐ and β‐Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

et al. 2017

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Presented herein is a study of the acid‐induced demetalation of two sterically hindered copper corroles, Cu β‐octabromo‐meso‐triphenylcorrole (Cu[Br8TPC]) and β‐octakis(trifluoromethyl)‐meso‐tris(p‐methoxyphenyl)corrole (Cu[(CF3)8TpOMePC]). Unlike reductive demetalation, which affords the free‐base β‐octabromocorrole, demetalation of Cu[Br8TPC] under non‐ reductive conditions (CHCl3/H2SO4) resulted in moderate yields of free‐base 5‐ and 10‐hydroxy isocorroles. The isomeric free bases could be complexed to CoII and NiII, affording stable complexes. Only reductive demetalation was found to work for Cu[(CF3)8TpOMePC], affording a highly saddled, hydrated corrole, H3[5‐OH,10‐H‐(CF3)8TpOMePC], where the elements of water had added across C5 and C10. Interaction of this novel free base with CoII resulted in Co[iso‐10‐H‐[CF3)8TpOMePC], a CoII 10‐hydro isocorrole. The new metal complexes were all characterized by single‐crystal X‐ray diffraction analysis and, despite their sterically hindered nature, were found to exhibit almost perfectly planar isocorrole cores.

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Section: Synthesis Of Co II [Iso-10-oh-br 8 Tpc](pph 3 )mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

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β‐Octabromo‐ and β‐Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands

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Synthesis and Characterization of Ruffled Phosphorus meso‐Ester Corroles

et al. 2016

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The strong electron-withdrawing character of 5,15meso-ester groups was demonstrated through the study of four fluorescent hexacoordinate phosphorus(V) meso-substituted corroles, which were characterized by various techniques including single-crystal X-ray diffraction and first-principles calcu- [a] Compound 4-P: To a solution of 10-octadecyl-5,15-bis(ethoxycarbonyl)corrole (13 mg, 0.02 mmol) in dry pyridine (5 mL) was added POCl 3 (0.19 mL, 2 mmol), and the reaction mixture was heated to reflux for 30 min under argon. The solution color changed immediately from deep green to purple-violet with a greenish tint. The progress of the reaction was monitored by TLC analysis, and its completion was determined by absorption spectroscopy. After the completion of the reaction, the solvent was evaporated under reduced pressure. The crude solid was purified by silica gel chromatography (CH 2 Cl 2 /CH 3 OH 50:1), and the desired compound was collected from a greenish pink-violet band. The solvent was evaporated to afford a deep purple-violet solid (66 %, 10 mg, 0.013 mmol). R f = 0.75 (silica, CH 2 ] + 725.3826; found 725.3826.Compound 5-P: To a solution of 3-P (15 mg, 0.02 mmol) in dry tetrahydrofuran (THF, 10 mL) was added NaBH 4 (7.6 mg, 0.2 mmol), and the reaction mixture was heated to reflux for 1 h under argon. The progress of the reaction was monitored by TLC analysis, and its completion was determined by absorption spectroscopy. After the completion of the reaction, the reaction was quenched with a H 2 O/ MeOH mixture. The mixture was extracted with CHCl 3 . The organic layer was washed with brine and dried with anhydrous Na 2 SO 4 , and the solvents were evaporated to dryness. The crude solid was purified by silica gel chromatography (CH 2 Cl 2 /EtOAc 20:1). Compound 5-P was crystallized from CH 2 Cl 2 /n-heptane to afford a purple solid (30 %, 4 mg, 6 μmol). R f = 0.38 (silica gel, CH 2 Cl 2 ).

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