Reactions of oxophlorines and their .pi. radicals

Fuhrhop, J.‐H.; Besecke, S.; Subramanian, J.; Mengersen, Chr.; Riesner, Detlev

doi:10.1021/ja00857a029

Cited by 83 publications

(45 citation statements)

References 13 publications

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“…3. In this molecule, Fe(III) is reduced to Fe(II) intramolecularly by transfer of one electron from the enolate anion >O- (4,19,25) (Fig. 1, spectrum a yielding spectra b).…”

Section: Resultsmentioning

confidence: 99%

“…Oxygen was added to reaction mixtures by injecting a calculated volume of an aqueous solution through a septum. Carbon monoxide was determined quantitatively with a Drager tube (19). Synthesis of the Four Benzoyloxyprotohemin Isomers.…”

Section: Methodsmentioning

confidence: 99%

“…Iron was inserted into each benzoyloxyprotoporphyrin IX dimethyl ester as previously described (21) and the chloride salt was crystallized from ethyl acetate. The pyridine hemochrome of the a isomer showed absorption maxima (CHC13) at 422 (e 153,600), 524(17,500), and 557 nm (19,400). Alkaline hydrolysis of each benzoyloxyprotohemin dimethyl ester to the oxyprotohemin was carried out according to the method of Sano et al (18).…”

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confidence: 99%

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On the mechanism of the chemical and enzymic oxygenations of alpha-oxyprotohemin IX to Fe.biliverdin IX alpha.

Sano¹,

Sano²,

Morishima³

et al. 1986

Proc. Natl. Acad. Sci. U.S.A.

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“…3. In this molecule, Fe(III) is reduced to Fe(II) intramolecularly by transfer of one electron from the enolate anion >O- (4,19,25) (Fig. 1, spectrum a yielding spectra b).…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

On the mechanism of the chemical and enzymic oxygenations of alpha-oxyprotohemin IX to Fe.biliverdin IX alpha.

Sano¹,

Sano²,

Morishima³

et al. 1986

Proc. Natl. Acad. Sci. U.S.A.

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“…These com pounds exhibit a special feature in that a single meso-oxo function allows for the existence of the tautom eric keto and enol forms [4]. In con trast to this, dioxo-porphyrins allow only the for m ulation o f ketonic structures which leads to in terruption o f the conjugated system [5,6], Due to this fact the dioxo-porphyrins were formerly called dioxo-porphodimethenes [7], This makes the 5,15-and 5,10-dioxo-porphyrins interesting ligands for coordination studies. So far, only the struc ture of a thallium (III) derivative of 5,15-dioxo-2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) had been reported by us [8].…”

Section: Introductionmentioning

confidence: 99%

“…The dis ordered positions and hydrogen atoms have been omit ted for clarity. (4) 145 (8) 3713 (6) 2603 (6) 27(4) C (5) 1169 (8) 4058 (6) 2129 (6) 27(4) C (6) 1678 (8) 3355 (6) 1514 (6) 25(3) C (7) 2450 ( (15) 1091 (4) 2014 (5) 3450 (4) 23(2) C (16) 2219 (4) 1776 (5) 2746 (4) 22 (2) C (17) 3314 (4) 1129 (5) 3221 (4) 26 (2) C (171) 3452 (5) 583 (6) 4514 (4) 43(3) C (18) 4204 (4) 1133 (5) 2258 (5) 30(3) C ( 181) 5511 (4) 602 (5) 2303 (5) 36(3) C (182) 6093 (5) 1551 (5) 2203 (5) 48(3) C (19) 3633 (4) 1716 (4) 1209 (4) 20 (2) C (20) 4239 (4) 1914(5) -7 (5) 26 (2) 0(1) 1180 (5) 3742 (6) -3569 (5)…”

Section: Introductionunclassified

Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I

Senge

1993

Zeitschrift Für Naturforschung B

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The crystal structures of two zinc(II) 5,15-dioxo-porphyrins (porphodimethenes) have been determined to investigate the coordination chemistry of porphyrins with interrupted conjuga tion system. Both com pounds have a five-coordinated zinc center with pyridine as axial ligand and show overall structural parameters very similar to porphyrins. The oxidized meso-posi tions are, however, easily identified by longer Cm-C a bond lengths and smaller Ca-C m-C a angles. The macrocycles exhibit a small degree of conform ational distortion, and the etiopor-

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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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Reactions of oxophlorines and their .pi. radicals

Cited by 83 publications

References 13 publications

On the mechanism of the chemical and enzymic oxygenations of alpha-oxyprotohemin IX to Fe.biliverdin IX alpha.

On the mechanism of the chemical and enzymic oxygenations of alpha-oxyprotohemin IX to Fe.biliverdin IX alpha.

Metal Complexes of Dioxo-porphyrins-Zinc(II) Complexes of 2,3,7,8,12,13,17,18-Octaethyl-5,15-dioxo-porphyrin and 5,15-Dioxo-etioporphyrin I

Iron Porphyrin Chemistry

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