Activation Volumes for a Series of Spontaneous, Acidand Base-Catalysed Aquation Reactions of Aniono trans- [Co(MeNH2)(NH3)4X]2,1+ Complexes (X=Cl-, Br-,ΝO3-,SO42-)
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Fabian Benzo
Abstract
The volumes of activation for the spontaneous, base-, and acid- catalysed path of the hydrolysis reaction of a series of trans-[Co(MeNH2)(NH3)4X](3-n)+ ions (X = Cl-, Br-, (ONO2)- (OSO3)2-) have been determined in order to establish analogies with the dissociative trends found in previous work with the spontaneous hydrolysis of neutral ligands from the same cores. While for the base catalysed path a significant decrease in the activation volume is found on going from the {Co(NH3)5} to the trans- {Co(MeNH2)(NH3)4} inert skeleton (i.e. 9.8, 12.5, 4.0 and 9.1 cm3 mol-1 for the chloro, bromo, nitrato and sulfato derivatives), no significant changes are observed for the same complexes in the spontaneous reaction. The trends are rationalized in terms of the important changes occurring in electrostriction factors for the DCB and Id intimate mechanisms operating and the important increase in the degree of dissociativeness due to the presence of a trans-methylamino ligand. For the acid catalysed path the differences are much more difficult to assess, specially taking into account the limited information available as well as the inherent errors involved in the rate constant determination.
© 2014 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Introducing The New Co-Editor Of Inorganic Reaction Mechanisms
- Kinetic and Mechanistic Studies of Substitution Reactions of Solvated Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Ions with 2,2′:6′,2″-Terpyridine and Several 2,2′:6′,2″-Terpyridine Derivatives. Evidence for the Formation of Intermediates
- Activation Volumes for a Series of Spontaneous, Acidand Base-Catalysed Aquation Reactions of Aniono trans- [Co(MeNH2)(NH3)4X]2,1+ Complexes (X=Cl-, Br-,ΝO3-,SO42-)
- Interactions of the Aminoglycoside Neamine and 2-Deoxystreptamine with Copper(II) and Zinc(II)
- Kinetics of Oxidative Deamination and Decarboxylation of L-Asparagine by Alkaline Permanganate: a Mechanistic Approach
- Kinetics of Magnesium Incorporation into Water Soluble Porphyrins
- Micellar Effect on Chromium(VI) Oxidation of D-Glucose in the Presence and Absence of Picolinic Acid in Aqueous Media: A Kinetic Study
- Kinetics of Oxidation of Antimony(III) by Tetrachloroaurate(III) in Aqueous Hydrochloric Acid Media
