KH(O2)CO2⋅H2O2 – ein sauerstoffreiches Salz der Monoperoxokohlensäure

Adam, Arnold; Mehta, Mathias

doi:10.1002/(sici)1521-3757(19980518)110:10<1457::aid-ange1457>3.0.co;2-d

Cited by 10 publications

(3 citation statements)

References 18 publications

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“…However, besides O 2 2- in basic molten carbonate, the direct observation or convincing in-situ spectroscopic identification of other active oxygen species (O 2 - / CO 4 2- or C 2 O 6 2- ) in the molten carbonate is scarce. Furthermore, the CO 4 2- and C 2 O 6 2- are also very concerned in many other fields. − In this work, we present the first spectroscopic identification of peroxocarbonate species in acidic molten carbonate by using the in-situ Raman spectroscopic technique.…”

Section: Introductionmentioning

confidence: 99%

First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate

et al. 2004

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An active oxygen species in molten carbonate is the key to elucidate the complex mechanism of the cathode reaction in MCFC. However, under acidic condition of MCFC operation (P CO 2 > 1.01 × 10 4 Pa), the exact chemical state of the active oxygen species remains unclear and is a subject of continuous debates. In this work, we present the first experimental observation of peroxocarbonate/peroxodicarbonate species in acidic molten carbonate by using in-situ Raman spectroscopic technique. The results indicate that the predominant oxygen species (O 2 2-) in basic lithium-rich melts became unstable with the increase of acidity level in the melts and reacted with CO 2 to produce peroxocarbonate or peroxodicarbonate anion. In combination with the result of theoretical calculation, it is deduced that the peroxodicarbonate mechanism is the dominant feature in the cathode reaction path in MCFC.

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Section: Introductionmentioning

confidence: 99%

First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate

et al. 2004

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“…36 1-Zn-O 2 is also a type of π-complex. In 1-Zn-O 2 , the lone electron pair of the terminal O atom, rather than the π electron in the oxo-osmium(IV) complex above, 37 of dioxygen donates an electron pair to a zinc d-orbital to form a σ-coordination bond (Figure 4a-I). The The bond parameters of the axial ligands in 1-Zn and 3-Zn fully support the above analysis ( Figure 3).…”

mentioning

confidence: 99%

“…1 -Zn-O 2 is also a type of π-complex. In 1 -Zn-O 2 , the lone electron pair of the terminal O atom, rather than the π electron in the oxo-osmium(IV) complex above, of dioxygen donates an electron pair to a zinc d-orbital to form a σ-coordination bond (Figure a-I). The metal consequently donates electron density back from a different filled d-orbital into the empty antibonding orbital (π*) of dioxygen (Figure a-II) to form a π-coordination bond (named a feedback π bond).…”

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confidence: 99%

Fixation of Zinc(II) Ion to Dioxygen in a Highly Deformed Porphyrin: Implications for the Oxygen Carrier Mechanism of Distorted Heme

Zhou

Liu

et al. 2015

Org. Lett.

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Three saddle-type nonplanar zinc porphyrins strapped by two short alkyl linkers have been synthesized. The deformation induced by the linkers can cause a spectral red shift of >30 nm compared with the absorption maxima of regular porphyrins and can also regulate the electronic structure of the central zinc(II) ion. The zinc(II) ion then complexes and activates a free dioxygen to form a superoxide group ligand by enlarging the splitting of energy levels of d orbitals under strong core deformation. The fixation of dioxygen can be reasonably explained by the Dewar-Chatt-Duncanson model. These results indicate that this type of saddle porphyrin has the potential to be used as a new model system of heme.

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A New Mononuclear Iron(III) Complex Containing a Peroxocarbonate Ligand

et al. 2002

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Peroxo iron(iii) complexes have been proposed as key intermediates in various oxidation reactions catalyzed by mononuclear non-heme iron enzymes and their functional model complexes. [1] Various types of synthetic mononuclear peroxo ± iron(iii) complexes with h 2 -peroxo, [2, 3] h 1 -hydroperoxo, [3,4] and alkylperoxo [5] ligands have been characterized by spectroscopic studies. However, there is no structurally characterized mononuclear peroxo iron(iii) complex to date. It has been shown that the structure, electronic structure, and reactivity of the peroxo complexes can be modified by the coordination environment at an iron(iii) center. For instance, a tetradentate tripod ligand, tris(2-pyridylmethyl)amine (TPA), has been shown to form a low-spin h 1 -hydroperoxo species, whereas sterically bulky TPA derivatives with 6-methyl groups give low-spin and/or high-spin alkylperoxo species. [5d] Furthermore, interconversion between h 2 -peroxo and h 1hydroperoxo species has been also observed in some complexes, where a change in spin states (high spin and low spin) also occurs. [1c, 3] Most of these peroxo ± iron(iii) complexes have nitrogen-rich coordination environments, except for the ethylenediaminetetraacetate (EDTA) complex. Thus, it is of interest to investigate how the nature of the donor atoms and the stereochemistry of the supporting ligands influence the formation, structure, and properties of such peroxo ± iron(iii) complexes. Here, we report the synthesis of a novel mononuclear iron(iii) complex with a bidentate peroxocarbonate ligand in a carboxylate-rich coordination environment, [Fe(qn) 2 (O 2 C(O)O)]Ph 4 P ¥ 1.5 CH 3 OH ¥ 0.5 (CH 3 ) 2 NCHO (1; see Figure 1), derived from the reaction of a bis(m-hydroxo)diiron(iii) complex, [Fe 2 (qn) 4 (OH) 2 ] ¥ 2 H 2 O (2) with H 2 O 2 and CO 2 , where Hqn is quinaldic acid. Compound 1 is the first 2 H; CH 2 ), 1.68 (m, 1 H; CH), 1.10 (s, 3 H; CH 3 ), 1.05 (s, 3 H; CH 3 ), and 0.95 (s, 3 H; CH 3 ); 13 C NMR (75 MHz, CDCl 3 , 258C): d

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KH(O2)CO2⋅H2O2 – ein sauerstoffreiches Salz der Monoperoxokohlensäure

Cited by 10 publications

References 18 publications

First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate

First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate

Fixation of Zinc(II) Ion to Dioxygen in a Highly Deformed Porphyrin: Implications for the Oxygen Carrier Mechanism of Distorted Heme

A New Mononuclear Iron(III) Complex Containing a Peroxocarbonate Ligand

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