Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents

Hayashi, Takashi; Nakashima, Y.; Ito, Kazuyuki; Ikegami, Takahiro; Aritome, Isao; Aoyagi, Katsuhiro; Ando, Takuya; Hisaeda, Yoshio

doi:10.1021/ic034757d

Cited by 28 publications

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“…Compounds 1 and 2-Cl were prepared in the same manner as in previous studies. 11 The compounds 3 and 4-Cl were prepared as described in the literature. 17 Compound 5-Cl was prepared by a modified method.…”

Section: Methodsmentioning

confidence: 99%

“…11 The corresponding monomeric complex 2-Cl was not available because the formation of the -oxo dimer was preferable even under the neutral conditions. After the treatment of CF 3 COOH/HClaq for over 30 min at room temperature, the monomeric 2-Cl was obtained, however, further purification of the monomeric complex was difficult, because 2-Cl was easily converted into the -oxo dimer 1 again in the solution.…”

Section: Synthesis and Characterization Of [{Fementioning

confidence: 99%

“…[2][3][4] In contrast, it is well-known that the introduction of electron-withdrawing groups at the peripheral position of the porphyrin framework stabilizes its LUMO energy level of the macrocycle. [5][6][7][8][9] Thus, it seems interesting to introduce electron-withdrawing groups at the peripheral positions of the porphycene to obtain an electron-deficient macrocycle, [10][11][12][13][14] although almost all porphycenes have only simple alkyl side chains as peripheral substituents such as methyl, ethyl, or butyl groups on the framework. [15][16][17] To further stabilize the LUMO energy level of porphycene, we have recently prepared the trifluoromethylated porphycene, 2,7,12,17-tetraethyl-3,6,13,16-tetrakis(trifluoromethyl)porphycene, Etio(CF 3 ) 4 PcH 2 .…”

mentioning

confidence: 99%

“…In addition, we initially determined that its iron -oxo complex, [{Fe III Etio(CF 3 ) 4 Pc} 2 -(-O)] (1), was readily converted into a monomeric iron(III) species, [Fe III Etio(CF 3 ) 4 Pc(py) 2 ] (2-Py 2 ), via the Fe-O bond cleavage and then reduced to a iron(II) complex in pyridine solution. 11,18 In this paper, we wish to utilize iron porphycenes without any electron-withdrawing groups, [ (6), to discuss the mechanisms of the unusual fast Fe-O bond cleavage and the following autoreduction of 1 (Chart 1).…”

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Isolable Iron(II)–Porphycene Derivative Stabilized by Introduction of Trifluoromethyl Groups on the Ligand Framework

Ito

Matsuo

Aritome

et al. 2008

Bulletin of the Chemical Society of Japan

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Two iron porphycene complexes having four trifluoromethyl groups, chloro-2,7,12,17-tetraethyl-3,6,13,16-tetrakis-(trifluoromethyl) characterized. The -oxo dimer was easily converted into the monomeric iron(II) complex via the Fe-O bond cleavage in pyridine. This is the first study to obtain a stable iron(II) species in a series of porphycene iron complexes. The iron(II) species crystallized in the monoclinic system C2=m, and the Fe-N pyridyl (2.007 Å ) and Fe-N pyrrolyl (1.958 Å ) bonds were remarkably short distances among the bispyridine-coordinated iron(II) porphyrins and porphyrinoids. To evaluate the influences of the CF 3 substituents and framework structure on the autoreduction, we compared the reactivity of It is of particular interest to compare the structure, physicochemical properties, and chemical reactivities of metalloporphycenes with those of metalloporphyrins, because the porphycene is a structural isomer of porphyrin with decrease in its framework symmetry from D 4h to D 2h .

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis and Characterization Of [{Fementioning

confidence: 99%

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Isolable Iron(II)–Porphycene Derivative Stabilized by Introduction of Trifluoromethyl Groups on the Ligand Framework

Ito

Matsuo

Aritome

et al. 2008

Bulletin of the Chemical Society of Japan

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“…A search of the Cambridge Structural Database (Version 5.26 of November 2004;Allen, 2002) found 36 structurally characterized -oxo-bridged dinuclear iron compounds in which the remaining coordination sites around the Fe atoms are occupied by a macrocyclic N 4 donor ligand. The ligand systems are generally similar to naturally occurring ligands such as porphyrin, porphycene, phthalocyanine or corrole (for the most recent examples, see Hayashi et al, 2003;Cheng et al, 2004;Litvinov et al, 2003;Chang et al, 2004;Lee et al, 2003;Baba et al, 2004;Ercolani et al, 1983;Simkhovich et al, 2001). In general, the corresponding bond lengths in -hydroxobridged compounds are significantly longer [1.821 (8)-1.952 (2) Å ; Scheidt et al, 1992;Evans et al, 1997].…”

Section: Commentmentioning

confidence: 99%

μ-Oxo-bis[(diethyl 6,17-dimethyldibenzo[a,h]-5,9,14,18-tetraaza[14]annulene-7,16-dicarboxylato)iron(III)] sesquihydrate

2006

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The title compound (systematic name: μ‐oxo‐bis{[4,15‐bis(ethoxycarbonyl)‐5,14‐dimethyl‐2,7,13,17‐tetraazatricyclo[16.4.0.07,12]docosa‐3,5,7,9,11,13,15,18(1),19,21‐decaene‐2,17‐diido]iron(III)} sesquihydrate), [Fe2(C26H26N4O4)O]·1.5H2O, crystallizes in the monoclinic space group C2/c and has two iron centres which are coordinated by macrocyclic ligands with an N4 donor set. These iron centres are bridged by a μ‐oxo ligand, resulting in the formation of a dinuclear complex unit. The μ‐oxo ligand interacts with a water molecule via strong hydrogen bonds. These solvent molecules aggregate by additional hydrogen bonds, producing a tetranuclear aggregate. Towards the outer rim of the cavity formed by the carboxyethyl substituents attached to the tetraaza‐annulene systems there are additional solvent molecules. Due to much weaker hydrogen‐bond interactions, the latter are disordered and have site‐occupancy factors less than 1.

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Iron Porphyrin Chemistry

Walker¹,

Simonis²

2005

Encyclopedia of Inorganic Chemistry

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This article reviews most aspects of the chemistry of iron porphyrins, from Fe(0) to Fe(V), including occurrence and roles of natural iron porphyrins (hemes) and their synthetic analogs, structures and electron configurations of iron porphyrins of all oxidation and spin states, π electron configuration of the porphyrin ring, synthesis of metal‐free porphyrins and other related macrocycles, insertion of iron into free‐base porphyrins and related macrocycles, the properties, reactions, uses and biological relevance of iron(0), ‐(I), ‐(II) porphyrins (the latter with S = 0, 1, and 2 spin state possibilities), of iron(II) porphyrin π‐cation radicals, of iron(III) porphyrins (with S = 1/2, 3/2, and 5/2 spin state possibilities), of iron(III) porphyrin and corrole π‐cation radicals, of iron(IV) porphyrins (including five‐ and six‐coordinate ferryl (FeO) 2+ , iron(IV) phenyl, carbene and hydrazine complexes, and the bis‐methoxide complex) and a comparison of iron(IV) porphyrins to iron(III) porphyrin π‐cation radicals, of iron(IV) porphyrin π‐cation radicals, and of the possible existence of iron(V) porphyrins. Included in the Fe(II) part are sections on addition of ligands to four‐coordinate iron(II) porphyrins, including equilibrium binding constants, photodissociation of ligands from PFeL 2 complexes, binding of small molecules (O 2 , CO, NO, HNO) to 5‐coordinate iron(II) porphyrins and design of porphyrin ligands that will mimic the active sites of heme proteins such as myoglobin and hemoglobin, the cytochromes P450 and nitric oxide synthases, and the nitrophorins and guanylyl cyclases. Included in the iron(III) part are sections on both 5‐ and 6‐coordinate high‐spin complexes and their similarities and differences, bridged or through‐space magnetically coupled complexes of high‐spin iron(III) porphyrins with other metal complexes as possible models for cytochrome oxidase and the assimilatory sulfite reductases, coupled oxidation of hemes by hydrogen peroxide or its equivalent, and the relationship of this reactivity to the reactions of heme oxygenase, iron(III) porphyrins as reduction catalysts, and photochemistry of iron(III) porphyrins, possible electron configurations of low‐spin iron(III) porphyrins, the phenomenon and possible electronic consequences of ruffling of the porphinato core in iron(III) porphyrins, the preferred orientation of planar axial ligands bound to low‐spin iron(III) porphyrins, NO complexes of iron(III) porphyrins, reduction potentials, equilibrium constants and rates of axial‐ligand addition and exchange, kinetics of axial‐ligand rotation and porphyrin ring inversion, kinetics of reduction and autoreduction of iron(III) porphyrins, electron self‐exchange between low‐spin iron(III) and iron(II) porphyrins, synthetic ferriheme proteins, and synthesis of five‐coordinate low‐spin iron(III) porphyrins having σ‐alkyl or σ‐aryl groups as axial ligands. The iron(IV) and iron(IV) cation radical sections discuss the high‐valent states of cytochromes P450 and related enzymes.

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Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents

Cited by 28 publications

References 19 publications

Isolable Iron(II)–Porphycene Derivative Stabilized by Introduction of Trifluoromethyl Groups on the Ligand Framework

Isolable Iron(II)–Porphycene Derivative Stabilized by Introduction of Trifluoromethyl Groups on the Ligand Framework

μ-Oxo-bis[(diethyl 6,17-dimethyldibenzo[a,h]-5,9,14,18-tetraaza[14]annulene-7,16-dicarboxylato)iron(III)] sesquihydrate

Iron Porphyrin Chemistry

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