Addition-Elimination or Nucleophilic Substitution? Understanding the Energy Profiles for the Reaction of Chalcogenolates with Dichalcogenides.
We have quantum chemically explored the mechanism of the substitution reaction between CH3X(-) and the homo- and heterodichalcogenides CH3X'X″CH3 (X, X', X″ = S, Se, Te) using relativistic density functional theory at ZORA-OLYP/TZ2P and COSMO for simulating the effect of aqueous solvation. In the gas phase, all substitution reactions proceed via a triple-well addition-elimination mechanism that involves a stable three-center intermediate. Aqueous solvation, in some cases, switches the character of the mechanism to double-well SN2 in which the stable three-center intermediate has become a labile transition state. We rationalize reactivity trends and some puzzling aspects of these elementary reactions, in particular, vanishing activation energies and ghost three-center intermediates, using the activation strain model (ASM).
Dipartimento di Scienze Chimiche, Università degli Studi di Padova , Via Marzolo 1, 35129 Padova, Italy.
Marco
M
Bortoli
Dipartimento di Scienze Chimiche, Università degli Studi di Padova , Via Marzolo 1, 35129 Padova, Italy.
Lando P
LP
Wolters
Dipartimento di Scienze Chimiche, Università degli Studi di Padova , Via Marzolo 1, 35129 Padova, Italy.
Laura
L
Orian
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.|Institute for Molecules and Materials (IMM), Radboud University , Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
F Matthias
FM
Bickelhaupt