Octahedral cobalt(III) complexes of the chloropentammine type. XVIII. Hydrolysis of some Chloroanilinebis(ethylenediamine)cobalt(III) complexes, and a rationalization for the conjugate-base and ion-pair mechanisms

1969 ◽  
Vol 22 (9) ◽  
pp. 1851 ◽  
Author(s):  
SC Chan ◽  
OW Lau
Keyword(s):  
Chloride Ion ◽  
Ion Pair ◽  
Base Hydrolysis ◽  
Methyl Substituent ◽  
Substituted Anilines ◽  
First Order ◽  
Base Mechanism ◽  
Higher Temperature ◽  
Hydrolysis Of ◽  
Conjugate Base

The kinetics for the appearance of chloride ion from aqueous solutions of the cis-chloroanilinebis(ethylenediamine)cobalt(III) cation are determined over the pH ranges of 2-3 at 40.0� and of 8-9 at 0�. By using self-buffered mixtures, the rate constants for the reaction are also measured at 40.0� as a function of the concentration of complex or of free aniline. The results are discussed in terms of the conjugate- base mechanism. A rationalization of this mechanism and the ion-pair mechanism is proposed to incorporate the base hydrolysis of other previously investigated systems where the complexes are decidedly much less acidic. At a higher temperature (65.0�), both chloride ion and aniline are liberated at similar rates, and the process is treated as parallel first-order reactions. By using complexes with meta- and para-substituted anilines, the effect of the methyl substituent on reactivity is studied.

Octahedral cobalt(III) complexes of the chloropentammine type. XX. The preparation, properties, and reactions of some chlorocycloalkylaminebis- (ethylenediamine)cobalt(III) salts

1970 ◽  
Vol 23 (4) ◽  
pp. 707 ◽  
Author(s):  
SC Chan ◽  
TL Cheung
Keyword(s):  
Rate Constants ◽  
Ion Pair ◽  
Base Hydrolysis ◽  
Isomeric Form ◽  
Visible Absorption ◽  
First Order ◽  
Order Rate ◽  
Hydrolysis Of ◽  
Conjugate Base ◽  
Visible Absorption Spectroscopy

Salts of one isomeric form of the chlorocycloalkylaminebis(ethylenediamine)cobalt(111) series of cations have been prepared and characterized. They are tentatively assigned a cis configuration on the basis of visible absorption spectroscopy. The first-order rate constants for the solvolytic aquation of these cations have been determined at 50.5�, and the results suggest the presence of steric acceleration. The second-order rate constants for the base hydrolysis of these cations have also been determined at 0� and ionic strength of 0.1M. These results are discussed in terms of the conjugate-base/ion-pair mechanistic spectrum postulated previously.

Base hydrolysis of trans-Halogenoamminebis(dimethylglyoximato) (III). Complexes

1969 ◽  
Vol 22 (12) ◽  
pp. 2569 ◽  
Author(s):  
SC Chan ◽  
PY Leung
Keyword(s):  
Equilibrium Constants ◽  
Base Hydrolysis ◽  
Hydroxide Ion ◽  
First Order ◽  
Rate Determining Step ◽  
Rapid Formation ◽  
Pseudo First Order ◽  
Conjugate Bases ◽  
Hydrolysis Of ◽  
Conjugate Base

The disappearance of trans-[Co(LH)2(NH3)X] (LH = dimethylglyoximate ion, X = chloride or bromide) has been studied in aqueous solutions over a range of alkali concentrations at various temperatures. The kinetics were done with excess of hydroxide ion at a constant ionic strength so that pseudo first-order rate constants were obtained in all the runs. The results were interpreted in terms of the rapid formation of a pre- equilibrium species which then reacts in a rate-determining step to give products. The relatively large equilibrium constants support a conjugate-base pre-equilibrium, in which the proton is lost from oxygen, while the relatively low reactivities of the conjugate-bases are consistent with the absence of electropositive electromeric effects. The similarity in the reactivities of the chloro and the bromo conjugate-bases suggests the possibility of an SN2CB mechanism.

Volumes of Activation for the Base Hydrolysis of [Rh(NH3)5X]2+ Complex Ions

1979 ◽  
Vol 32 (12) ◽  
pp. 2589 ◽  
Author(s):  
DA Palmer
Keyword(s):  
Partial Molar Volumes ◽  
Base Hydrolysis ◽  
Volume Data ◽  
Complex Ions ◽  
Molar Volumes ◽  
Base Mechanism ◽  
Hydrolysis Of ◽  
Conjugate Base

The pressure dependencies of the rates of base hydrolysis of [Rh(NH3)5X]2+ were measured at 313.2 K and μ1M, where X = Cl-, Br-, I- and NO3-, in the range 1-1500 bar. The respective Δν‡exp values are 19.3 � 0.9, 20.2 � 0.5, 20.4 � 0.5 and 22.3 � 0.9cm3 mol-1. The partial molar volumes of these complexes, as well as those of other relevant pentaamminerhodium(III) complexes, were also determined. The volume data are discussed in terms of the conventional dissociative conjugate base mechanism. The Δν‡exp for the aquation of [Rh(NH3)5NO3]2+ was found to be -6.9 � 0.4cm3 mol-1 at 313.2K, [H+] 0.005M and μ0.1 M. An I mechanism is favoured for this process.

Protodemercuration of organomercuric chlorides. II. Heterocyclic mercuric chlorides

1965 ◽  
Vol 18 (10) ◽  
pp. 1513 ◽  
Author(s):  
RD Brown ◽  
AS Buchanan ◽  
AA Humffray
Keyword(s):  
Chloride Ion ◽  
Ion Pair ◽  
Zero Order ◽  
Hydrogen Ion ◽  
First Order ◽  
Entropy Effects ◽  
Kinetics Of ◽  
Complex Anions ◽  
Dominant Influence ◽  
Electron Effects

The kinetics of protodemercuration, or displacement of the HgCl group by hydrogen, have been measured for 2- and 3-furyl, 2-thienyl, and 2-selenophenylmercuric chlorides. The reactions of these compounds with aqueous alcoholic hydrochloric acid were first order in hydrogen ion, first order in RHgC1, and zero order in chloride ion, when the latter was present at concentrations less than 0.1M. At 70�, the relative rates were: 3-furyl, 1; 2-furyl, 27; 2-thienyl, 11; 2-seleno- phenyl, 25. At higher chloride concentrations, the rate increases; this is discussed in terms of formation of complex anions of the type RHgCl32- and in terms of H+Cl- ion pair attack. The dominant influence of entropy effects in the case of furan compounds emphasizes the danger of trying to account for observed relative rates in terms of π-electron effects alone.

The trans-Effect in Octahedral Complexes. VI. Base Hydrolysis of trans-Hydroxybromo and trans-Hydroxychlorobis(ethylenediamine)-rhodium(III) Complexes

1975 ◽  
Vol 53 (12) ◽  
pp. 1842-1848 ◽  
Author(s):  
Anthony Poë ◽  
Carol Vuik
Keyword(s):  
Rate Equation ◽  
Base Hydrolysis ◽  
Small Contribution ◽  
Trans Effect ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Order Rate Equation

The kinetics of base hydrolysis of the complexes trans-[Rh(en)2(OH)X]+ (X = Br or Cl) follow the pseudo first order rate equation kobs = k1 + k2[OH−]. The small contribution of the [OH−]-dependent term is due to lower values of ΔS2≠ − ΔS1≠ than are observed for the complexes cis-[Rh(en)2(OH)Cl]+ and [Rh(NH3)5X]2+ (X = Cl, Br, or I ). The values of ΔH1≠ are used to obtain new values of the intrinsickinetictrans-effect (i.k.t.e.) of hydroxide that agree with that determined from aquation of trans.-[Rh(en)2(OH)I]+ and place hydroxide in the i.k.t.e. series [Formula: see text] The new data also allow hydroxide to be placed in a thermodynamic trans-effect (t.t.e.) series I > OH > NH3 > Br > Cl > OH2, and the different position of hydroxide in the two series is discussed.

cis-Activation by Oxyanions Coordinated to Chromium(III): Aquation and Base Hydrolysis of Nitratopentaamminechromium(III) Ion

1974 ◽  
Vol 52 (4) ◽  
pp. 527-535 ◽  
Author(s):  
Giovanni Guastalla ◽  
Thomas Wilson Swaddle
Keyword(s):  
Reaction Rate ◽  
Base Hydrolysis ◽  
Alkaline Solutions ◽  
Acidic Solutions ◽  
First Order ◽  
Order Rate ◽  
Rate Of Hydrolysis ◽  
Pseudo First Order ◽  
Hydrolysis Of

The aquation of Cr(NH3)5NO32+ in acidic solutions yields not only Cr(NH3)5OH23+ (33%) but also more highly aquated species including cis-Cr(NH3)4(OH2)23+ and Cr(NH3)3(OH2)33+. In 0.1 M HClO4, several successive reactions of comparable rates are involved, but at pH 6 only the two competing initial reactions producing Cr(NH3)5OH2+ and cis-Cr(NH3)4(OH)NO3+ are rate-controlling, so that the overall reaction rate is first-order in substrate with the apparent parameters kA = 2.4 × 10−3 s−1(25°), ΔHA* = 20.4 kcal mol−1, and ΔSA* = −2.1 cal deg−1 mol−1. In alkaline solutions, the pseudo-first-order rate of hydrolysis at a given [OH−] is governed by kobs = kA + kOH [OH−], with kOH = 1.1 × 10−2 M−1 s−1 (25°), ΔHOH* = 25.2 kcal mol−1, and ΔSOH* = 17.0 cal deg−1 mol−1. The path characterized by kOH leads exclusively to Cr(NH3)5OH2+. In both aquation and base hydrolysis, it is the Cr—ONO2 bond that is broken. The production of more highly aquated species in the aquation reactions is attributed to transient chelation of NO3− at the expense of a ligand cis to it. The evidence for this mechanism, and for its operation when oxyanions other than nitrate are coordinated to Cr(III), is reviewed.

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