Complexation of sterically hindered cobalt porphyrin with 1-methylimidazole along the axial coordinate and the reaction of reversible binding of oxygen

Valiotti, A. B.; Abakumova, R. A.

doi:10.1007/s11167-005-0084-7

Cited by 2 publications

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“…While the binding of dioxygen to cobalt porphyrins is well-known, much of the data reported was gathered at low temperatures (below −20 °C) either in solution − or in frozen solutions. , There are relatively few cobalt porphyrins capable of reversibly binding dioxygen at ambient temperatures, most notably cobalt substituted myoglobins , and the aforementioned cobalt “picket fence” porphyrin meso -α,α,α,α-tetrakis( o -pivalamidophenyl) porphyinatocobalt(II). This porphyrin binds dioxygen at room temperature in solution − and in the solid state, but only when a basic axial ligand is present. Kinetic data on the adsorption/desorption of dioxygen to this molecule have been reported at 40 °C, wherein a two-stage adsorption model was proposed …”

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confidence: 99%

Single Molecule Imaging of Oxygenation of Cobalt Octaethylporphyrin at the Solution/Solid Interface: Thermodynamics from Microscopy

et al. 2012

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For the first time, the pressure and temperature dependence of a chemical reaction at the solid/solution interface is studied by scanning tunneling microscopy (STM), and thermodynamic data are derived. In particular, the STM is used to study the reversible binding of O(2) with cobalt(II) octaethylporphyrin (CoOEP) supported on highly oriented pyrolytic graphite (HOPG) at the phenyloctane/CoOEP/HOPG interface. The adsorption is shown to follow the Langmuir isotherm with P(1/2)(298K) = 3200 Torr. Over the temperature range of 10-40 °C, it was found that ΔH(P) = -68 ± 10 kJ/mol and ΔS(P) = -297 ± 30 J/(mol K). The enthalpy and entropy changes are slightly larger than expected based on solution-phase reactions, and possible origins of these differences are discussed. The big surprise here is the presence of any O(2) binding at room temperature, since CoOEP is not expected to bind O(2) in fluid solution. The stability of the bound oxygen is attributed to charge donation from the graphite substrate to the cobalt, thereby stabilizing the polarized Co-O(2) bonding. We report the surface unit cell for CoOEP on HOPG in phenyloctane at 25 °C to be A = (1.46 ± 0.1)n nm, B = (1.36 ± 0.1)m nm, and α = 54 ± 3°, where n and m are unknown nonzero non-negative integers.

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Section: Introductionmentioning

confidence: 99%

Single Molecule Imaging of Oxygenation of Cobalt Octaethylporphyrin at the Solution/Solid Interface: Thermodynamics from Microscopy

et al. 2012

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Kinetics of n-propylmercaptan oxidation by cobalt(III) octahydroxyphthalocyanine in an alkali medium

et al. 2016

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Complexation of sterically hindered cobalt porphyrin with 1-methylimidazole along the axial coordinate and the reaction of reversible binding of oxygen

Abstract: The complexation of a sterically hindered cobalt porphyrin with 1-methyl imidazole and its reaction of reversible binding of oxygen was studied. Spectrophotometry and potentiometry were used to determine the equilibrium constant of the oxygenation process.

Cited by 2 publications

References 3 publications

Single Molecule Imaging of Oxygenation of Cobalt Octaethylporphyrin at the Solution/Solid Interface: Thermodynamics from Microscopy

Single Molecule Imaging of Oxygenation of Cobalt Octaethylporphyrin at the Solution/Solid Interface: Thermodynamics from Microscopy

Kinetics of n-propylmercaptan oxidation by cobalt(III) octahydroxyphthalocyanine in an alkali medium

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