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- Associative_substitution abstract "Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to coordination and organometallic complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms.Associative pathways are characterized by binding of the attacking (nucleophile) to give a discrete, detectable intermediate followed by loss of another ligand. Complexes that undergo associative substitution are either coordinatively unsaturated or contain a ligand that can change its bonding to the metal, e.g. change in hapticity or bending of NO. In homogeneous catalysis, the associative pathway is desirable because the binding event, and hence the selectivity of the reaction, depends not only on the nature of the metal catalyst but also on the substrate.Examples of associative mechanisms are commonly found in the chemistry of 16e square planar metal complexes, e.g. Vaska's complex and tetrachloroplatinate. These compounds (MX4) bind the incoming (substituting) ligand Y to form pentacoordinate intermediates MX4Y that in a subsequent step dissociates one of their ligands. Dissociation of Y results in no reaction, but dissociation of X results in net substitution, giving the 16e complex MX3Y. The first step is typically rate determining. Thus, the entropy of activation is negative, which indicates an increase in order in the system. These reactions follow second order kinetics: the rate of the appearance of product depends on the concentration of MX4 and Y. The rate law is governed by the Eigen–Wilkins Mechanism.".
- Associative_substitution thumbnail AssveRxn.png?width=300.
- Associative_substitution wikiPageID "21789230".
- Associative_substitution wikiPageLength "9046".
- Associative_substitution wikiPageOutDegree "33".
- Associative_substitution wikiPageRevisionID "646834589".
- Associative_substitution wikiPageWikiLink Associative_substitution.
- Associative_substitution wikiPageWikiLink Avogadro_constant.
- Associative_substitution wikiPageWikiLink Category:Chemical_reactions.
- Associative_substitution wikiPageWikiLink Category:Coordination_chemistry.
- Associative_substitution wikiPageWikiLink Category:Organometallic_chemistry.
- Associative_substitution wikiPageWikiLink Category:Reaction_mechanisms.
- Associative_substitution wikiPageWikiLink Category:Substitution_reactions.
- Associative_substitution wikiPageWikiLink Cation.
- Associative_substitution wikiPageWikiLink Conjugate_acid.
- Associative_substitution wikiPageWikiLink Conjugate_base.
- Associative_substitution wikiPageWikiLink Coordination_complex.
- Associative_substitution wikiPageWikiLink Coordinatively_unsaturated.
- Associative_substitution wikiPageWikiLink Dissociative_substitution.
- Associative_substitution wikiPageWikiLink Entropy_of_activation.
- Associative_substitution wikiPageWikiLink Gas_constant.
- Associative_substitution wikiPageWikiLink Hapticity.
- Associative_substitution wikiPageWikiLink Homogeneous_catalysis.
- Associative_substitution wikiPageWikiLink Hydrolysis.
- Associative_substitution wikiPageWikiLink Indene.
- Associative_substitution wikiPageWikiLink Indenyl_effect.
- Associative_substitution wikiPageWikiLink Ion.
- Associative_substitution wikiPageWikiLink Ligand.
- Associative_substitution wikiPageWikiLink Manfred_Eigen.
- Associative_substitution wikiPageWikiLink Naphthalene.
- Associative_substitution wikiPageWikiLink Nucleophile.
- Associative_substitution wikiPageWikiLink Organic_chemistry.
- Associative_substitution wikiPageWikiLink Organometallic_chemistry.
- Associative_substitution wikiPageWikiLink Potassium_tetrachloroplatinate.
- Associative_substitution wikiPageWikiLink SN1_reaction.
- Associative_substitution wikiPageWikiLink SN2_reaction.
- Associative_substitution wikiPageWikiLink Saturation_(chemistry).
- Associative_substitution wikiPageWikiLink Sn1CB_mechanism.
- Associative_substitution wikiPageWikiLink Thiocyanate.
- Associative_substitution wikiPageWikiLink Vacuum_permittivity.
- Associative_substitution wikiPageWikiLink Vaskas_complex.
- Associative_substitution wikiPageWikiLink File:AssveRxn.png.
- Associative_substitution wikiPageWikiLinkText "Associative substitution".
- Associative_substitution wikiPageWikiLinkText "Eigen–Wilkins Mechanism".
- Associative_substitution wikiPageWikiLinkText "associative interchange".
- Associative_substitution wikiPageWikiLinkText "associative ligand substitution".
- Associative_substitution wikiPageWikiLinkText "associative mechanism".
- Associative_substitution wikiPageWikiLinkText "associative substitution".
- Associative_substitution wikiPageWikiLinkText "associative".
- Associative_substitution wikiPageWikiLinkText "ligand substitution".
- Associative_substitution hasPhotoCollection Associative_substitution.
- Associative_substitution wikiPageUsesTemplate Template:Eqm.
- Associative_substitution wikiPageUsesTemplate Template:Reflist.
- Associative_substitution subject Category:Chemical_reactions.
- Associative_substitution subject Category:Coordination_chemistry.
- Associative_substitution subject Category:Organometallic_chemistry.
- Associative_substitution subject Category:Reaction_mechanisms.
- Associative_substitution subject Category:Substitution_reactions.
- Associative_substitution type Process.
- Associative_substitution type Reaction.
- Associative_substitution comment "Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to coordination and organometallic complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to Sn1 pathway.".
- Associative_substitution label "Associative substitution".
- Associative_substitution sameAs Eigen-Wilkins-Mechanismus.
- Associative_substitution sameAs Sustitución_asociativa.
- Associative_substitution sameAs m.05mqxph.
- Associative_substitution sameAs Q1303017.
- Associative_substitution sameAs Q1303017.
- Associative_substitution wasDerivedFrom Associative_substitution?oldid=646834589.
- Associative_substitution depiction AssveRxn.png.
- Associative_substitution isPrimaryTopicOf Associative_substitution.