Volumes of activation for the anation of Pd(II) substituted dien complexes by chloride ion in aqueous solution. A high pressure stopped-flow instrument for studying the kinetics of fast reactions under pressure

Eldik, Rudi van; Palmer, Donald A.; Schmidt, Reinhard H.; Kelm, H.

doi:10.1016/s0020-1693(00)83732-9

Cited by 122 publications

(38 citation statements)

References 15 publications

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“…Measurements at high pressure were carried out using a homemade high-pressure stopped-flow unit. [48] Kinetic data were analyzed with the OLIS KINFIT (Bogart, GA, USA) program. All instruments used were thermostated to the desired temperature (Ϯ 0.1°C).…”

Section: Methodsmentioning

confidence: 99%

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

Alzoubi

Hamza

Dücker-Benfer

et al. 2002

Eur. J. Inorg. Chem.

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The ligand substitution reactions of trans-[Co III (en) 2 (Me)H 2 O] 2+ and trans-[Co III (en) 2 (Me)NH 3 ] 2+ were studied for CN − , SCN − , N 3 − , and NH 3 as entering nucleophiles. These nucleophiles displace the coordinated H 2 O and NH 3 molecules trans to the methyl group and form the sixcoordinate complex trans-[Co(en) 2 (Me)L]. The complexformation constant for the displacement of H 2 O by NH 3 was found to be 17.4 ± 1.1 M −1 at 20°C, and those for the displacement of NH 3 by SCN − and N 3 − were found to be 4.4 ± 1.5 and 3.1 ± 0.4 at 10°C, respectively. From temperature and pressure dependence studies, activation parameters (∆H ϶ , ∆S ϶ and ∆V ϶ ) for the reaction of trans-[Co III (en) 2 (Me)H 2 O] 2+

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Section: Methodsmentioning

confidence: 99%

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

Alzoubi

Hamza

Dücker-Benfer

et al. 2002

Eur. J. Inorg. Chem.

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“…High pressure stopped-flow experiments were performed in the pressure range of 10 to 130 MPa on a custombuilt apparatus. [48] OLIS KINFIT software (Bogart, GA, 1989) was used for the analysis of kinetic traces.…”

Section: Kinetic Measurementsmentioning

confidence: 99%

Mechanistic Insight into Peroxo‐Shunt Formation of Biomimetic Models for Compound II, Their Reactivity toward Organic Substrates, and the Influence of N‐Methylimidazole Axial Ligation

Oszajca¹,

Drzewiecka-Matuszek²,

Franke³

et al. 2014

Chemistry A European J

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High-valent iron-oxo species have been invoked as reactive intermediates in catalytic cycles of heme and nonheme enzymes. The studies presented herein are devoted to the formation of compound II model complexes, with the application of a water soluble (TMPS)Fe(III)(OH) porphyrin ([meso-tetrakis(2,4,6-trimethyl-3-sulfonatophenyl)porphinato]iron(III) hydroxide) and hydrogen peroxide as oxidant, and their reactivity toward selected organic substrates. The kinetics of the reaction of H2O2 with (TMPS)Fe(III)(OH) was studied as a function of temperature and pressure. The negative values of the activation entropy and activation volume for the formation of (TMPS)Fe(IV)=O(OH) point to the overall associative nature of the process. A pH-dependence study on the formation of (TMPS)Fe(IV)=O(OH) revealed a very high reactivity of OOH(-) toward (TMPS)Fe(III)(OH) in comparison to H2O2. The influence of N-methylimidazole (N-MeIm) ligation on both the formation of iron(IV)-oxo species and their oxidising properties in the reactions with 4-methoxybenzyl alcohol or 4-methoxybenzaldehyde, was investigated in detail. Combined experimental and theoretical studies revealed that among the studied complexes, (TMPS)Fe(III)(H2O)(N-MeIm) is highly reactive toward H2O2 to form the iron(IV)-oxo species, (TMPS)Fe(IV)=O(N-MeIm). The latter species can also be formed in the reaction of (TMPS)Fe(III)(N-MeIm)2 with H2O2 or in the direct reaction of (TMPS)Fe(IV)=O(OH) with N-MeIm. Interestingly, the kinetic studies involving substrate oxidation by (TMPS)Fe(IV)=O(OH) and (TMPS)Fe(IV)=O(N-MeIm) do not display a pronounced effect of the N-MeIm axial ligand on the reactivity of the compound II mimic in comparison to the OH(-) substituted analogue. Similarly, DFT computations revealed that the presence of an axial ligand (OH(-) or N-MeIm) in the trans position to the oxo group in the iron(IV)-oxo species does not significantly affect the activation barriers calculated for C-H dehydrogenation of the selected organic substrates.

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“…High-pressure stopped-flow experiments were performed on a custom-built instrument described previously [13,14] at pressures up to 130 MPa. The kinetic traces were recorded at 424 nm on an IBM-compatible PC and analyzed with the OLIS KINFIT (Bogart, GA, 1989) set of programs.…”

Section: Instrumentationmentioning

confidence: 99%

The role of positively charged meso-substituents on the kinetics of the reductive nitrosylation of iron(III)-porphyrins

Theodoridis

Eldik

2004

Journal of Molecular Catalysis A: Chemical

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Volumes of activation for the anation of Pd(II) substituted dien complexes by chloride ion in aqueous solution. A high pressure stopped-flow instrument for studying the kinetics of fast reactions under pressure

Cited by 122 publications

References 15 publications

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

Mechanistic Insight into Peroxo‐Shunt Formation of Biomimetic Models for Compound II, Their Reactivity toward Organic Substrates, and the Influence of N‐Methylimidazole Axial Ligation

The role of positively charged meso-substituents on the kinetics of the reductive nitrosylation of iron(III)-porphyrins

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