title: Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley.
abstract: β-Hydride eliminations for ethylgold(III) dichloride complexes are identified as reactions with an unusually long prechemical stage corresponding to the conformational preparation of the reaction complex and spanning six phases. The prechemical process is characterized by a geared rotation of the L-Au-L group (L = Cl) driving methyl group rotation and causing a repositioning of the ligands. This requires more than 28 kcal/mol of the total barrier of 34.0 kcal/mol, according to the unified reaction valley approach, which also determines that the energy requirements of the actual chemical process leading to the β-elimination product are only about 5.5 kcal/mol. A detailed mechanistic analysis was used as a basis for a rational design of substrates (via substituents on the ethyl group) and/or ligands, which can significantly reduce the reaction barrier. This strategy takes advantage of either a higher trans activity of the ligands or a tuned electronic demand of the ethyl group. The β-hydride elimination of gold(I) was found to suffer from strong Coulomb and exchange repulsion when a positively charged hydrogen atom enforces a coordination position in a d(10)-configured gold atom, thus triggering an unassisted σ-π Au(I)-C conversion.
authors.affiliation: Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
authors.forename: Marta
authors.initials: M
authors.lastname: Castiñeira Reis
authors.affiliation: Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
authors.forename: Carlos Silva
authors.initials: CS
authors.lastname: López
authors.affiliation: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University (SMU) , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Elfi
authors.initials: E
authors.lastname: Kraka
authors.affiliation: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University (SMU) , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Dieter
authors.initials: D
authors.lastname: Cremer
authors.affiliation: Departamento de Química Orgánica, Universidade de Vigo, Campus As Lagoas , 32004 Ourense, Spain.
authors.forename: Olalla Nieto
authors.initials: ON
authors.lastname: Faza