Iron porphycene

Hayashi T, Dejima H, Matsuo T et al (2002) Blue myoglobin reconstituted with an iron porphycene shows extremely high oxygen affinity. J Am Chem Soc 124 11226-11227... 

Hayashi T, Murata D, Makino M (2006) Crystal structure and peroxidase activity of myoglobin reconstituted with iron porphycene. Inorg Chem 45 10530-10536... 

Oxoiron(IV) tefraphenylchlorin complexes have been prepared as the first models of a reaction intermediate in the catalytic cycle of cytochrome d Optical absorption spectra show a characteristic red-shified band at 630 nm as observed in the oxoferryl intermediate of cytochrome d, and the proton NMR spectra of the N-Melm complex exhibit very small hyperfine shifts of the pyrrole protons, as is true for oxoferryl porphyrin complexes. The pyrroline protons of the saturated pyrrole ring show unusual splitting into upheld and downfield resonances. The N-Melm complex also shows normal Fe =0 stretching frequencies as compared to the corresponding oxoferryl porphyrin complexes. And finally, for iron porphycenes, both peroxo and ferryl intermediates have been detected by H NMR spectroscopy during the oxygenation of the Fe complexes. ... 

Trematode species from paramphistomum epiclitum. At 25 °C, pH 7.0. Sperm whale. Horse heart. Myoglobin reconstituted with an iron porphycene. At 25 °C, pH 7.0. 

Successful structural analyses of artificial metalloproteins have been reported [5, 6, 17, 22]. Hayashi et al. have determined the crystal structure of a reconstituted apo-Mb with the iron porphycene derivative 13,16-dicarboxyethyl-2,7-diethyl-3,6,12,17-tetramethylporphycenato-Fe " (iron porphycene) [22], The structure shows... 

Only a handful of rr-bonded iron porphyrin complexes have been structurally characterized, listed in Table HI, and four of these contain porphycene. corrolc. or phthalocyanine ligands rather than porphyrins. " "" Selected data arc given in Table III, and X-ray crystal structures of methyl- and phenyliron porphyrin complexes are shown in Fig. 4. All of the iron(III) porphyrin complexes exhibit... 

Porphycenes (150) and corrphycenes (151) are porphyrin isomers, several of whose iron(III) complexes have been characterized. Examples include distorted square-pyramidal (12,17-diethox-ycarbonyl-2,3,6,7,1 l,18-hexamethylcorrphycenato)iodo-iron(III), [Fe(tprpc)X] (where tprpc = 2,7, 12,17-tetra-u-propylporphycene) with X = C1, Br, N3, 02CMe, or OPh and [Fe(tprpc)2]0. " Iron(II)- and iron(IV)-tproc complexes also exist, as established in an examination of oxygenation of iron(II) porphycene.The structure of chloro(3,6,13,16-tetraethyl-2,7,12,17-tetramethylpor-phycenato)iron(III), also distorted square-pyramidal, has been compared with those of chloro-iron(III) porphyrin complexes. ... 

Matsuo T, Murata D, Hisaeda Y, Hori H, Hayashi T (2007) Porphyrinoid chemistry in hemoprotein matrix detection and reactivities of iron(IV)-oxo species of porphycene incorporated into horseradish peroxidase. J Am Chem Soc 129 12906-12907... 

Several other examples of porphycene complexes with trivalent metals have also appeared in the literature.3.4.12,29,29-32 These include the aluminum(III) complexes 3.75a-d and 3.76, as well at the manganese(III), cobalt(III) iron(III), indium(III), and gallium(III) complexes 3.77-3.81 (Figure 3.1.16). Interestingly, a p-oxo-dialuminum(III)porphycenate 3.85 analogous to the p-oxo-diiron(III)porphycenates 3.72 and 3.73 has also been prepared. This was accomplished by heating the aluminum(III)porphycenato hydroxide complex 3.76 to 350 °C under reduced pressure (Scheme 3.1.12). 

Iron(III) porphycenes readily form /r-oxo dimers, and a complex having tetra-CFs etioporphycene was investigated by X-ray crystallography, electrochemistry and solution... 

In a similar manner, the first examples of iron metalloporphycenes [(EtioPc)FeArj 138 with a-bonded aryl groups have been synthesized (EtioPc = dianion of 2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycene) (Scheme 23). Since the porphycene macrocycle is isomeric with the porphyrin cycle, a comparison of the electrochemical behavior to... 

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