Synthese, Struktur und Komplexierungseigenschaften von partiell und vollständig reduzierten<i>meso</i>‐Octamethylporphyrinogenen (Calix[4]pyrrolen)

Blangy, Valeria; Heiss, Christoph; Khlebnikov, V. A.; Letondor, Christophe; Stœckli-Evans, Helen; Neier, Reinhard

doi:10.1002/ange.200804937

Cited by 17 publications

(13 citation statements)

References 41 publications

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“…For the synthesis of (II), 2,2 0 -(propane-2,2-diyl)bis(1H-pyrrole), (I) (Journot, Letondor et al, 2010;Blangy et al, 2009) (5.00 g, 29 mmol), 10% Pd/C (1.30 g), methanol (20 ml) and acetic acid (2 ml) were placed in an autoclave vessel. The reaction was kept under hydrogen (50 atm; 1 atm = 101 325 Pa) and stirred at room temperature for 20 h. The reaction mixture was then filtered through a pad of Celite and washed three times with dichloromethane.…”

Section: Methodsmentioning

confidence: 99%

“…In order to study the selectivity of the hydrogenation (monohydrogenation versus total hydrogenation) and to compare the hydrogenation conditions of the dipyrromethane 2,2 0 -(propane-2,2-diyl)bis(1H-pyrrole), (I) , with the hydrogenation conditions of calix[4]pyrrole (Blangy et al, 2009;Journot, Letondor et al, 2010), the synthesis and crystal structure of the partially reduced compound 2-[2-(pyrrolidin-2-yl)propan-2-yl]-1Hpyrrole, (II), were studied. During efforts to modify partially reduced calix[4]pyrroles (Blangy et al, 2009;Journot, Letondor et al, 2010) by introducing amides on the pyrrolidine rings, unforeseen difficulties were encountered.…”

Section: Commentmentioning

confidence: 99%

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2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone

2012

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In the title compounds, C(11)H(18)N(2), (II), and C(13)H(20)N(2)O, (III), the pyrrolidine rings have twist conformations. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. The mean planes of the pyrrole and pyrrolidine rings are inclined to one another by 89.99 (11) and 89.35 (10)° in molecules A and B, respectively. In (III), the amide derivative of (II), the same dihedral angle is much smaller, at only 13.42 (10)°. In the crystal structure of (II), the individual molecules are linked via N-H...N hydrogen bonds to form inversion dimers, each with an R(2)(2)(12) graph-set motif. In the crystal structure of (III), the molecules are linked via N-H...O hydrogen bonds to form inversion dimers with an R(2)(2)(16) graph-set motif.

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Section: Methodsmentioning

confidence: 99%

Section: Commentmentioning

confidence: 99%

2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone

2012

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“…Calix [4]pyrrolidine 1 [12] (80 mg, 0.18 mmol, 1 equiv.) and MnA C H T U N G T R E N N U N G (OAc) 2 ·4 H 2 O (44 mg, 0.18 mmol, 1 equiv.)…”

Section: General Procedures For the Preparation Of Mn Complexes 2 Andmentioning

confidence: 99%

“…During our studies of the hydrogenation of calix [4]pyrroles we were able to isolate the fully reduced porphyrinogen macrocycle 1 (Scheme 1), able to function as a non-porphyrin ligand for metal binding. [12] Although fully saturated, this novel tetraaza-macrocycle shows a "disc-like", almost planar conformation in the crystal. The four basic nitrogen atoms were shown to function as efficient chelating ligands for transition metals such as Cu, Ni, Pd, with the four pyrrolidine N À H bonds pointing in a parallel direction orthogonal to the plane of the disk.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle

et al. 2012

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The present paper details the first application of a fully reduced meso-octamethylporphyrinogen macrocycle as an effective ligand for simple operative manganese-catalyzed alkene epoxidation. The efficiency of the novel catalyst was determined in the presence of various oxidants, apical ligands and acidic/basic additives. Higher reactivity was found in favour of electron-rich alkenes, whereas an electron-deficient conjugated alkene appeared as a poor substrate in the screening. Sulfur additives were active as apical ligands, whereas nitrogen-containing additives influenced the reactivity only moderately. cis-Stilbene and 3b-acetoxy-5-cholestene were epoxidized in a stereoselective manner. The X-ray structures of the new manganese complexes were determined and showed a rigid planar coordination geometry of the saturated macrocyclic ligand to the metal centre.

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“…Calixpyrroles can bind anions efficiently (Sessler et al, 2000), but they coordinate transition metals only under forcing conditions (Jubb et al, 1992;Floriani, 1996;Bonomo et al, 2001). Recently we reported on the partial and complete reduction of meso-octamethylporphyrinogen, or calix [4]pyrrole as it is called (Blangy et al, 2009;Journot et al, 2010). It was found that the reduced form of calix[4]pyrrole, i.e.…”

Section: Introductionmentioning

confidence: 99%

Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex

2014

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The title compound, tetrachlorido-1κCl;2κ(3)Cl-(2,2,7,7,12,12,17,17-octamethyl-21,22,23,24-tetraazapentacyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosane-1κ(4)N,N',N'',N''')-μ2-oxido-diiron(III), [Fe2Cl4O(C28H52N4)], undergoes a slow phase transformation at ca 173 K from monoclinic space group P2(1)/n, denoted form (I), to the maximal non-isomorphic subgroup, triclinic space group P1, denoted form (II), which is accompanied by nonmerohedral twinning [twin fractions of 0.693 (4) and 0.307 (4)]. The transformation was found to be reversible, as on raising the temperature the crystal reverted to monoclinic form (I). In the asymmetric unit of form (I), Z' = 1, while in form (II), Z' = 2, with a very small reduction (ca 1.8%) in the unit-cell volume. The two independent molecules (A and B) in form (II) are related by a pseudo-twofold screw axis along the b axis. The molecular overlay of molecule A on molecule B has an r.m.s. deviation of 0.353 Å, with the largest distance between two equivalent atoms being 1.202 Å. The reaction of calix[4]pyrrolidine, the fully reduced form of meso-octamethylporphyrinogen, with FeCl3 gave a red-brown solid that was recrystallized from ethanol in air, resulting in the formation of the title compound. In both forms, (I) and (II), the Fe(III) atoms are coordinated to the macrocyclic ligand and have distorted octahedral FeN4OCl coordination spheres. These Fe(III) atoms lie out of the mean plane of the four N atoms, displaced towards the O atom of the [OFeCl3] unit by 0.2265 (5) Å in form (I), and by 0.2210 (14) and 0.2089 (14) Å, respectively, in the two independent molecules (A and B) of form (II). The geometry of the [OFeCl3] units are similar, with each Fe(III) atom having a tetrahedral coordination sphere. The NH H atoms are directed below the planes of the macrocycles and are hydrogen bonded to the coordinated Cl(-) ions. There are also intramolecular C-H···Cl hydrogen bonds present in both (I) and (II). In form (I), there are no significant intermolecular interactions present. In form (II), the individual molecules are arranged in alternate layers parallel to the ac plane. The B molecules are linked by a C-H···Cl hydrogen bond, forming chains along [100].

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Synthese, Struktur und Komplexierungseigenschaften von partiell und vollständig reduziertenmeso‐Octamethylporphyrinogenen (Calix[4]pyrrolen)

Cited by 17 publications

References 41 publications

2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone

2-[2-(Pyrrolidin-2-yl)propan-2-yl]-1H-pyrrole and its amide derivative 1-{2-[2-(1H-pyrrol-2-yl)propan-2-yl]pyrrolidin-1-yl}ethanone

Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle

Phase-transformation-induced twinning of an iron(III) calix[4]pyrrolidine complex

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