An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct.

An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Research Abstract Details 

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An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Abstract Text:

Eduardo E ,Kenneth D Karlin,

Side-on eta2-peroxo-iron porphyrins are strong nucleophiles. In cytochrome P450-like aromatase and other enzymes, such species are postulated as the active oxidants. In cytochrome c oxidase, hemea3-peroxo, hemea3-hydroperoxo, or hemea3-(mu-peroxo)-copper species are proposed as transient intermediates forming prior to O-O bond cleavage. In this report, we describe (1) a facile method for reduction of a heme-O2 species [(F8TPP)FeIII(O2-)(S)] (2), generating the ferric peroxo porphyrin complex [(F8TPP)FeIII(O22-)]- (3) (UV-vis, THF: lambdamax = 435 (Soret), 540(sh), 561; EPR: g = 8.7, 4.2), and (2) that this can be subsequently reacted with a ligand-copper(II) complex, [CuII(TMPA)-(CH3CN)](ClO4)2 (4), affording a heme-peroxo-copper heterobinuclear compound, [(F8TPP)FeII(O22-)-CuII(TMPA)](ClO4) (5). Generation of [(F8TPP)FeIII(O22-)]- (3) using cobaltocene as a one-electron reductant was monitored by UV-vis, EPR, and 1H NMR spectroscopies. Reaction between 3 and 4 was followed by UV-vis spectroscopy, and the product 5 could be precipitated and characterized. Coordination by copper(II) in 5 makes possible further reduction of the mu-peroxo complex by cobaltocene yielding the mu-oxo analogue, [(F8TPP)FeIII(O2-)-CuII(TMPA)](ClO4) (6).

An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Publishing Authors By Initials

EE ,KD Karlin,

For similar investigative techniques: chemistry, analytical: photometry: spectrophotometry: spectrophotometry, ultraviolet research abstracts see: investigative techniques: chemistry, analytical: photometry: spectrophotometry: spectrophotometry, ultraviolet research

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An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 125

Page Numbers: 16160-1

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 31

MONTH: Dec

YEAR: 2003

An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 7503056

An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Keywords Mesh Terms:

KEYWORDS: Spectrophotometry, Ultraviolet

MESH TERMS: chemical synthesis

Chemical & Substance for Abstract: An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct. Information

Substance Name: Copper

Registry Number: 7440-50-8

Grant and Affiliation Information for An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct.

AFFILIATION: Department of Chemistry, The Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM60353

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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