Tridentate copper ligand influences on heme-peroxo-copper formation and properties: Reduced, superoxo, and μ-peroxo iron/copper complexes

Eunsuk Kim, Matthew E. Helton, Shen Lu, Pierre Moenne-Loccoz, Christopher D. Incarvito, Arnold L. Rheingold, Susan Kaderli, Andreas D. Zuberbühler, Kenneth D. Karlin

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Abstract

In cytochrome c oxidase synthetic modeling studies, we recently reported a new μ-η22-peroxo binding mode in the heteronuclear heme/copper complex [(2L)FeIII-(O 2 2-)-CuII]+ (6) which is effected by tridentate copper chelation (J. Am. Chem. Soc. 2004, 126, 12716). To establish fundamental coordination and O2-reactivity chemistry, we have studied and describe here (i) the structure and dioxygen reactivity of the copper-free compound (2L)FeII (1), (ii) detailed spectroscopic properties of 6 in comparisons with those of known μ-η2: η1 heme-peroxo-copper complexes, (iii) formation of 6 from the reactions of [(2L)FeIICuI]+ (3) and dioxygen by stopped-flow kinetics, and (iv) reactivities of 6 with CO and PPh3. In the absence of copper, 1 serves as a myoglobin model compound possessing a pyridine-bound five-coordinate iron(II)-porphyrinate which undergoes reversible dioxygen binding. Oxygenation of 3 below -60°C generates the heme-peroxo-copper complex 6 with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) to yield an S = 2 spin system. Stopped-flow kinetics in CH2-Cl2/6% EtCN show that dioxygen reacts with iron(II) first to form a heme-superoxide moiety, [(EtCN)(2L)FeIII-(O2 -) ⋯CuI(EtCN)]+ (5), which further reacts with Cu I to generate 6. Compared to those properties of a known μ-η21-heme-peroxo-copper complex, 6 has a significantly diminished resonance Raman ν(O-O) stretching frequency at 747 cm-1 and distinctive visible absorptions at 485, 541, and 572 nm, all of which seem to be characteristics of a μ-η2: η2-heme-peroxo-copper system. Addition of CO or PPh3 to 6 yields a bis-CO adduct of 3 or a PPh3 adduct of 5, the latter with a remaining FeIII-(O2 -) moiety.

Original languageEnglish (US)
Pages (from-to)7014-7029
Number of pages16
JournalInorganic Chemistry
Volume44
Issue number20
DOIs
StatePublished - Oct 3 2005

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Heme
Copper
Iron
Ligands
iron
copper
ligands
Carbon Monoxide
Oxygen
reactivity
adducts
myoglobin
chelation
Kinetics
Oxygenation
Myoglobin
inorganic peroxides
oxygenation
oxidase
cytochromes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Tridentate copper ligand influences on heme-peroxo-copper formation and properties : Reduced, superoxo, and μ-peroxo iron/copper complexes. / Kim, Eunsuk; Helton, Matthew E.; Lu, Shen; Moenne-Loccoz, Pierre; Incarvito, Christopher D.; Rheingold, Arnold L.; Kaderli, Susan; Zuberbühler, Andreas D.; Karlin, Kenneth D.

In: Inorganic Chemistry, Vol. 44, No. 20, 03.10.2005, p. 7014-7029.

Research output: Contribution to journalArticle

Kim, E, Helton, ME, Lu, S, Moenne-Loccoz, P, Incarvito, CD, Rheingold, AL, Kaderli, S, Zuberbühler, AD & Karlin, KD 2005, 'Tridentate copper ligand influences on heme-peroxo-copper formation and properties: Reduced, superoxo, and μ-peroxo iron/copper complexes', Inorganic Chemistry, vol. 44, no. 20, pp. 7014-7029. https://doi.org/10.1021/ic050446m
Kim, Eunsuk ; Helton, Matthew E. ; Lu, Shen ; Moenne-Loccoz, Pierre ; Incarvito, Christopher D. ; Rheingold, Arnold L. ; Kaderli, Susan ; Zuberbühler, Andreas D. ; Karlin, Kenneth D. / Tridentate copper ligand influences on heme-peroxo-copper formation and properties : Reduced, superoxo, and μ-peroxo iron/copper complexes. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 20. pp. 7014-7029.
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abstract = "In cytochrome c oxidase synthetic modeling studies, we recently reported a new μ-η2:η2-peroxo binding mode in the heteronuclear heme/copper complex [(2L)FeIII-(O 2 2-)-CuII]+ (6) which is effected by tridentate copper chelation (J. Am. Chem. Soc. 2004, 126, 12716). To establish fundamental coordination and O2-reactivity chemistry, we have studied and describe here (i) the structure and dioxygen reactivity of the copper-free compound (2L)FeII (1), (ii) detailed spectroscopic properties of 6 in comparisons with those of known μ-η2: η1 heme-peroxo-copper complexes, (iii) formation of 6 from the reactions of [(2L)FeIICuI]+ (3) and dioxygen by stopped-flow kinetics, and (iv) reactivities of 6 with CO and PPh3. In the absence of copper, 1 serves as a myoglobin model compound possessing a pyridine-bound five-coordinate iron(II)-porphyrinate which undergoes reversible dioxygen binding. Oxygenation of 3 below -60°C generates the heme-peroxo-copper complex 6 with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) to yield an S = 2 spin system. Stopped-flow kinetics in CH2-Cl2/6{\%} EtCN show that dioxygen reacts with iron(II) first to form a heme-superoxide moiety, [(EtCN)(2L)FeIII-(O2 -) ⋯CuI(EtCN)]+ (5), which further reacts with Cu I to generate 6. Compared to those properties of a known μ-η2:η1-heme-peroxo-copper complex, 6 has a significantly diminished resonance Raman ν(O-O) stretching frequency at 747 cm-1 and distinctive visible absorptions at 485, 541, and 572 nm, all of which seem to be characteristics of a μ-η2: η2-heme-peroxo-copper system. Addition of CO or PPh3 to 6 yields a bis-CO adduct of 3 or a PPh3 adduct of 5, the latter with a remaining FeIII-(O2 -) moiety.",
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AU - Lu, Shen

AU - Moenne-Loccoz, Pierre

AU - Incarvito, Christopher D.

AU - Rheingold, Arnold L.

AU - Kaderli, Susan

AU - Zuberbühler, Andreas D.

AU - Karlin, Kenneth D.

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N2 - In cytochrome c oxidase synthetic modeling studies, we recently reported a new μ-η2:η2-peroxo binding mode in the heteronuclear heme/copper complex [(2L)FeIII-(O 2 2-)-CuII]+ (6) which is effected by tridentate copper chelation (J. Am. Chem. Soc. 2004, 126, 12716). To establish fundamental coordination and O2-reactivity chemistry, we have studied and describe here (i) the structure and dioxygen reactivity of the copper-free compound (2L)FeII (1), (ii) detailed spectroscopic properties of 6 in comparisons with those of known μ-η2: η1 heme-peroxo-copper complexes, (iii) formation of 6 from the reactions of [(2L)FeIICuI]+ (3) and dioxygen by stopped-flow kinetics, and (iv) reactivities of 6 with CO and PPh3. In the absence of copper, 1 serves as a myoglobin model compound possessing a pyridine-bound five-coordinate iron(II)-porphyrinate which undergoes reversible dioxygen binding. Oxygenation of 3 below -60°C generates the heme-peroxo-copper complex 6 with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) to yield an S = 2 spin system. Stopped-flow kinetics in CH2-Cl2/6% EtCN show that dioxygen reacts with iron(II) first to form a heme-superoxide moiety, [(EtCN)(2L)FeIII-(O2 -) ⋯CuI(EtCN)]+ (5), which further reacts with Cu I to generate 6. Compared to those properties of a known μ-η2:η1-heme-peroxo-copper complex, 6 has a significantly diminished resonance Raman ν(O-O) stretching frequency at 747 cm-1 and distinctive visible absorptions at 485, 541, and 572 nm, all of which seem to be characteristics of a μ-η2: η2-heme-peroxo-copper system. Addition of CO or PPh3 to 6 yields a bis-CO adduct of 3 or a PPh3 adduct of 5, the latter with a remaining FeIII-(O2 -) moiety.

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