1979
DOI: 10.1351/pac197951081713
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Solvents and their role in determining inorganic mechanisms

Abstract: -Two aspects of the mechanisms of the reactions of metal complexes in nonaqueous solutions are discussed in this paper. Firstly, the contribution made by studies in non-aqueous solvents, and in particular dipolar aprotic solvents, to the understanding of the mechanisms of substitution reactions at transition metal centres is considered. Secondly, the mechanisms of electron transfer reactions between transition metal centres are discussed with particular reference to recent work on the role of the solvent. THE … Show more

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Cited by 11 publications
(3 citation statements)
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“…Therefore the alkaline hydrolysis of esters, which is one of the most investigated secondorder model reactions in water and aqueous mixtures, is unsuited for the investigation of specific solvent effects despite many efforts 385 ~3 88 >. Most inorganic reactions of solvolysis and nucleophilic substitution of transition metal complexes are rather insensitive towards a change from protic to aprotic dipolar solvents 368) . Since the maximum coordination number of the complexes cannot be exceeded, in most cases the rate-determining step is a dissociation leaving a transition state with a positive charge almost one unit higher than the initial complex and an anion or, in few cases, a molecule.…”
Section: Kinetic Solvent Effectsmentioning
confidence: 99%
“…Therefore the alkaline hydrolysis of esters, which is one of the most investigated secondorder model reactions in water and aqueous mixtures, is unsuited for the investigation of specific solvent effects despite many efforts 385 ~3 88 >. Most inorganic reactions of solvolysis and nucleophilic substitution of transition metal complexes are rather insensitive towards a change from protic to aprotic dipolar solvents 368) . Since the maximum coordination number of the complexes cannot be exceeded, in most cases the rate-determining step is a dissociation leaving a transition state with a positive charge almost one unit higher than the initial complex and an anion or, in few cases, a molecule.…”
Section: Kinetic Solvent Effectsmentioning
confidence: 99%
“…Most inorganic reactions of solvolysis and nucleophilic substitution of transition metal complexes are rather insensitive towards a change from protic to aprotic dipolar solvents 368) . Since the maximum coordination number of the complexes cannot be exceeded, in most cases the rate-determining step is a dissociation leaving a transition state with a positive charge almost one unit higher than the initial complex and an anion or, in few cases, a molecule.…”
Section: E -• Products C=c + Br0^-c-c-(370(375] '^2mentioning
confidence: 99%
“…The general area of reaction kinetics and solvation in nonaqueous solvents has been reviewed by Caldin (53). Solvent effects on rates and mechanisms of transition metal complexes have been considered by Burgess ( 50 this topic, and points out that the role of solvents in determining inorganic mechanisms is much smaller than in carbon chemistry owing to solvolytic effects and to the counteracting of changes in anion solvation by changes in solvation of the cationic residue (314).…”
mentioning
confidence: 99%