title: High-pressure pulse-radiolysis study of the formation and decomposition of complexes with iron-carbon sigma bonds: mechanistic comparison for different metal centers.
abstract: Volumes of activation for the formation and homolysis of the transient complexes (hedta)Fe(III)-CO(2)(2-) and (hedta)Fe(III)-CH(3)(-) (HOCH(2)CH(2)N(CH(2)CO(2-))CH(2)CH(2)N(CH(2)CO(2-))(2) = hedta) were determined using high-pressure pulse-radiolysis techniques. A comparison of the results with those for analogous complexes with other central transition-metal cations (M(n+)) and ligands (L) points out that (i) the reaction of M(n)L(m) with aliphatic radicals (R(*)) proceeds via an interchange ligand substitution mechanism, i.e. M(n)L(m) + R(*) --> L(m-1)M(n+1)-R + L, (ii) the homolysis of the metal-carbon bonds naturally follows the same mechanism, and (iii) the volume of activation for the homolysis reaction depends strongly on the nature of the central cation, i.e. larger for M(n+1) = Cr(III), Co(III), Ni(III) and smaller for Fe(III). The volume of activation for the reaction (hedta)Fe(III)-CO(2)(2-) + CO(2)(*-) + 2H(+) --> Fe(II)(hedta)(H(2)O)(-) + CO + CO(2) was measured, and the results enable a tentative proposal for the nature of the transition state of this interesting reaction.
authors.affiliation: Department of Physical Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel.
authors.forename: S
authors.initials: S
authors.lastname: Goldstein
authors.forename: G
authors.initials: G
authors.lastname: Czapski
authors.forename: R
authors.initials: R
authors.lastname: van Eldik
authors.forename: N
authors.initials: N
authors.lastname: Shaham
authors.forename: H
authors.initials: H
authors.lastname: Cohen
authors.forename: D
authors.initials: D
authors.lastname: Meyerstein
mesh_terms: D002244:Carbon; D002384:Catalysis; D002614:Chelating Agents / Q000737:chemistry*; D004492:Edetic Acid / Q000031:analogs & derivatives* / Q000737:chemistry*; D007501:Iron; D007700:Kinetics; D008670:Metals; D008958:Models, Molecular; D008968:Molecular Conformation; D011675:Pulse Radiolysis
chemical_list: D002614:Chelating Agents; D008670:Metals; D002244:Carbon; D004492:Edetic Acid; D007501:Iron; C026060:N-(hydroxyethyl)ethylenediaminetriacetic acid