Kinetics of the solvolysis of trans-dichlorobis(1,2-diaminoethane)cobalt(III) ion in water and in water + propan-2-ol

Groves, Grahame S.; Wells, Cecil F.

doi:10.1039/f19827800619

Cited by 19 publications

(2 citation statements)

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“…On the other hand, the observed variations in the solvolysis rate in media of different relative permittivity suggest that the rate determining step of the reaction depends to some extent on the ionizing power of the medium. Plots of log k versus the interpolated [18,19] were also non-linear as shown in Figure 2. This non-linearity may arise from the differential effects in solvent structure and solvation with changes in solvent composition between the initial and transition states.…”

Section: Resultsmentioning

confidence: 99%

Influence of solvent structure on the aquation of trans-[Ru(3-MePy)4Cl2] complex in mixed aqueous solvents

Khalifa

Ismail

Soliman

2007

Transition Met Chem

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The kinetics of the solvolytic aquation of trans-[Ru (3-Me Py) 4 Cl 2 ] was studied spectrophotometrically in waterisopropanol in the range (30-90% v/v), and water acetonitrile in the range (10-70% v/v), and in the temperature range 50-65°C. Plots of log k versus the reciprocal of the relative permittivity and Grunwald-Winstien gave nonlinear plots. This non-linearity is derived from a large differential effect of solvent structure between the initial and transition states. The plot of log k versus water concentration was also non linear; evidence for the presence of a S N 1 mechanism. However, extrema in the variation of enthalpy DH* and entropy DS* of activation correlate well with the extrema in physical properties of the mixtures which are related to changes in solvent structure. Linear plots of DH* versus DS* were obtained and the iso-kinetic temperature indicates that the reaction is entropy controlled.

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Section: Resultsmentioning

confidence: 99%

Influence of solvent structure on the aquation of trans-[Ru(3-MePy)4Cl2] complex in mixed aqueous solvents

Khalifa

Ismail

Soliman

2007

Transition Met Chem

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“…It has long been recognized that the solvolysis reactions of Co(III) complexes [25,26], proceed via the Id mechanism [27,28] involving the rate-determining loss of the halide ion according to the following equations:…”

Section: Variation Of Free Energy Of Transfer With Solvent Compositionmentioning

confidence: 99%

Studies on ion-pairing effects of the kinetics of aquation of bromopentaammine cobalt(III) complex in malonate media

2011

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Medium effects on the initial and the transition states upon the solvolysis of trans‐dichlorobis(N‐methyl‐ethylenediamine)cobalt(III) complex in water‐mixed solvents

El‐Subruiti

2002

Int J of Chemical Kinetics

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The kinetics of solvolysis of trans-dichlorobis(N-methylethylenediamine)cobalt(III)complex have been investigated in aqua-organic solvent media (0-60% (v/v) cosolvent) at 25 ≤ t • C ≤ 60, using n-propanol and tert-butyl alcohol as cosolvents. The first-order rate constant increased nonlinearly with the reciprocal of the dielectric constant D s −1 , and x org , reflecting the individuality of the cosolvents and thereby suggesting that the relative stabilities of the transition state and initial state were governed by the preferential solvation effect. The thermodynamic parameters ( H = and S = ) were sensitive to the structural changes in the bulk solvent phase.

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Kinetics of the solvolysis of trans-dichlorobis(1,2-diaminoethane)cobalt(III) ion in water and in water + propan-2-ol

Cited by 19 publications

References 0 publications

Influence of solvent structure on the aquation of trans-[Ru(3-MePy)4Cl2] complex in mixed aqueous solvents

Influence of solvent structure on the aquation of trans-[Ru(3-MePy)4Cl2] complex in mixed aqueous solvents

Studies on ion-pairing effects of the kinetics of aquation of bromopentaammine cobalt(III) complex in malonate media

Medium effects on the initial and the transition states upon the solvolysis of trans‐dichlorobis(N‐methyl‐ethylenediamine)cobalt(III) complex in water‐mixed solvents

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