RT journal article
T1 Kinetic and DFT Studies on the Mechanism of C−S Bond Formation by Alkyne Addition to the [Mo3S4(H2O)9]4+ Cluster
A1 Pino-Chamorro, Jose Ángel
A1 García Algarra, Andrés
A1 Fernández-Trujillo Rey, María Jesús
A1 Hernández-Molina, Rita
A1 García Basallote, Manuel
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
AB Reaction of [Mo3(μ3-S)(μ-S)3] clusters with alkynes usually leads to formation of two C−S bonds between thealkyne and two of the bridging sulfides. The resulting compounds contain a bridging alkenedithiolate ligand, and the metal centers appear to play a passive role despite reactions at those sites being well illustrated for this kind of cluster. A detailed study including kinetic measurements and DFT calculations has been carried out to understand the mechanism of reaction of the [Mo3(μ3-S)(μ-S)3(H2O)9]4+ (1) cluster with two different alkynes, 2-butyne-1,4-diol and acetylenedicarboxylic acid. Stoppedflow experiments indicate that the reaction involves the appearance in a single kinetic step of a band at 855 or 875 nm, depending on the alkyne used, a position typical of clusters with two C−S bonds. The effects of the concentrations of the reagents, the acidity, and the reaction medium on the rate of reaction have been analyzed. DFT and TD-DFT calculations provide information on the nature of the product formed, its electronic spectrum and the energy profile for the reaction. The structure of the transition state indicates that the alkyne approaches the cluster in a lateral way and both C−S bonds are formed simultaneously.
PB ACS Publications
YR 2013
FD 2013-11
LK http://hdl.handle.net/10498/20483
UL http://hdl.handle.net/10498/20483
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 21-sep-2026