Cytochrome c oxidase models: a dinuclear iron(III) porphyrin-copper(II) complex with a sulfur bridge

Serr, Barbara R.; Headford, Christine E. L.; Anderson, Oren P.; Elliott, C. Michael; Spartalian, K.; Fainzil'berg, V.E.; Hatfield, William E.; Rohrs, Brian R.; Eaton, Gareth R.

doi:10.1021/ic00052a022

Cited by 28 publications

(12 citation statements)

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“…0.4 Å and relatively long Ga−N bonds (2.05 Å). The structural parameters are in the range found for a variety of gallium(III) porphyrins by X-ray crystallography. , The calculations indicate that two subunits of (TrPP) 2 (Ga III Cl) 2 are not necessarily orthogonal. The dimeric molecule has the C 2 symmetry with the C 2 axis perpendicular to the C(5)−C(5‘) bond, and the two (TrPP)Ga III subunits are equivalent.…”

Section: Resultsmentioning

confidence: 70%

¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

et al. 1999

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The 1H NMR spectra of iron(III) complexes of dimeric 5,5‘-bis(10,15,20-triphenylporphyrin) [(TrPPH2)2], 5,5‘-bis(10,15,20-tris(p-methoxyphenyl)porphyrin) [(Tr(p-MeOP)PH2)2], and hybrid (TrPPH2)(Tr(p-MeOP)PH2) and the respective monomeric 5,10,15-triphenylporphyrin (TrPPH2) and 5,10,15-tris(p-methoxyphenyl)porphyrin [Tr(p-MeOP)PH2] have been investigated in order to elucidate an impact of a direct meso − meso linkage on the electronic structure of corresponding high- and low-spin iron(III) porphyrins. The following species, covering the representative spin/oxidation states, have been investigated: (TrPP)2(FeIIICl)2 (high spin); [(TrPP)2(FeIII(CN)2)2]2- (low spin); [(TrPP)2(FeIIICl)2]+ (high-spin iron(III), diporphyrin radical); [(TrPP•)2(FeIIICl)2]2+ (high-spin iron(III), diradical of diporphyrin). The iron(III) diporphyrins (TrPP)2(FeIIICl)2, [(TrPP)2(FeIII(CN)2)2]2-, {[(TrPP)FeIII(CN)2][(Tr(p-MeOP)P)FeIII(CN)2]}2-, and [(TrPP)2(FeIIICl)2]2+ revealed the 1H NMR features which have been typically encountered in the spectra of the relevant monomeric complexes. Thus magnetic interactions between two subunits via skeleton appear to be minor. The characteristic broadening and/or paramagnetic shifts of 3-H and 7-H resonances were determined and are diagnostic features of the meso − meso linkage. One-electron, ligand-based oxidation of (TrPP)2(FeIIICl)2 to produce [(TrPP)2(FeIIICl)2]+ was observed with the unpaired electron delocalized over both macrocycles. The structure of (Tr(p-MeOP)P)ZnII·0.4CH2Cl2, the fundamental building block in synthesis of diporphyrins, was determined by X-ray crystallography. (Tr(p-MeOP)P)ZnII crystallizes in the monoclinic space group C2/c with a = 47.744(9) Å, b = 9.090(2) Å, c = 15.571(2) Å, β = 93.770(13)°, and Z = 8. The refinement of 494 parameters and 4361 reflections yields R 1 = 0.0756, wR 2 = 0.2169. The (Tr(p-MeOP)P)ZnII presents characteristic features of zinc(II) tetraphenylporphyrin. The molecular periphery of (Tr(p-MeOP)P)ZnII has a fully exposed meso position and two partially exposed pyrrole rings.

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Section: Resultsmentioning

confidence: 70%

¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

et al. 1999

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“…[65] The location of gallium almost in the macrocycle plane has been observed for the sixcoordinate gallium(III ) in the [(TPP)Ga III (THF) 2 ] cation (TPP: tetraphenylporphyrin dianion; THF: tetrahydrofuran). [66] In the series of the metallooxophlorin radicals including the oxophlorin dianion radicals, the variations in bond lengths were rather negligible, and resembled those found for (OEPO . )Fe III X.…”

Section: Tautomeric Equilibriamentioning

confidence: 56%

Oxophlorin and Metallooxophlorin Radicals—DFT Studies

Szterenberg¹,

Latos‐Grażyński²,

Wojaczyński³

2002

ChemPhysChem

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“…These examples show that balancing ligand contributions using BVS values will fail if the correct oxidation state does not give the best BVS ®t. The structures of the mixed Fe/Cu complexes FIHFEH (Brewer & Sinn, 1987) and YAKMIG (Serr et al, 1992) provide further examples of this, the Cu oxidation state being incorrect due to the default Fe R 0 values providing a poor ®t.…”

Section: Resultsmentioning

confidence: 99%

The assignment and validation of metal oxidation states in the Cambridge Structural Database

Shields

Raithby

Allen

et al. 2000

Acta Crystallogr B Struct Sci

132

101

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A methodology has been developed for the semi-automatic assignment and checking of formal oxidation states for metal atoms in the majority of metallo-organic complexes stored in the Cambridge Structural Database (CSD). The method uses both chemical connectivity and bond-length data, via ligand donor group templates and bond-valence sums, respectively. In order to use bond-length data, the CSD program QUEST has been modified to allow the coordination sphere of metal atoms to be recalculated using user-defined criteria at search time. The new methodology has been used successfully to validate the +1, +2 and +3 oxidation states in 743 four-coordinate copper complexes in the CSD for which atomic coordinates are available in ca 99% of structures using one or other method, and both succeed for >86% of structures.

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Cytochrome c oxidase models: a dinuclear iron(III) porphyrin-copper(II) complex with a sulfur bridge

Cited by 28 publications

References 0 publications

¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

Oxophlorin and Metallooxophlorin Radicals—DFT Studies

The assignment and validation of metal oxidation states in the Cambridge Structural Database

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Cytochrome c oxidase models: a dinuclear iron(III) porphyrin-copper(II) complex with a sulfur bridge

Cited by 28 publications

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1H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

1H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

Oxophlorin and Metallooxophlorin Radicals—DFT Studies

The assignment and validation of metal oxidation states in the Cambridge Structural Database

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Product

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¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)

¹H NMR Investigations of Triphenylporphyrin Metal Complexes and Electronic Interactions in Iron(III) Complexes of meso−meso-Linked 5,5‘-Bis(10,15,20-triphenylporphyrin)