title: Mechanism of [3+2] cycloaddition of alkynes to the [Mo3 S4 (acac)3 (py)3 ][PF6 ] cluster.
abstract: A study, involving kinetic measurements on the stopped-flow and conventional UV/Vis timescales, ESI-MS, NMR spectroscopy and DFT calculations, has been carried out to understand the mechanism of the reaction of [Mo3 S4 (acac)3 (py)3 ][PF6 ] ([1]PF6 ; acac=acetylacetonate, py=pyridine) with two RCCR alkynes (R=CH2 OH (btd), COOH (adc)) in CH3 CN. Both reactions show polyphasic kinetics, but experimental and computational data indicate that alkyne activation occurs in a single kinetic step through a concerted mechanism similar to that of organic [3+2] cycloaddition reactions, in this case through the interaction with one Mo(μ-S)2 moiety of [1](+) . The rate of this step is three orders of magnitude faster for adc than that for btd, and the products initially formed evolve in subsequent steps into compounds that result from substitution of py ligands or from reorganization to give species with different structures. Activation strain analysis of the [3+2] cycloaddition step reveals that the deformation of the two reactants has a small contribution to the difference in the computed activation barriers, which is mainly associated with the change in the extent of their interaction at the transition-state structures. Subsequent frontier molecular orbital analysis shows that the carboxylic acid substituents on adc stabilize its HOMO and LUMO orbitals with respect to those on btd due to better electron-withdrawing properties. As a result, the frontier molecular orbitals of the cluster and alkyne become closer in energy; this allows a stronger interaction.
authors.affiliation: Departmento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Instituto de Biomoléculas, Universidad de Cádiz, Avda. República Saharahui s/n, 11510 Puerto Real (Spain), Fax: (+34) 956-016-288.
authors.forename: Jose Ángel
authors.initials: JÁ
authors.lastname: Pino-Chamorro
authors.forename: Artem L
authors.initials: AL
authors.lastname: Gushchin
authors.forename: M Jesús
authors.initials: MJ
authors.lastname: Fernández-Trujillo
authors.forename: Rita
authors.initials: R
authors.lastname: Hernández-Molina
authors.forename: Cristian
authors.initials: C
authors.lastname: Vicent
authors.forename: Andrés G
authors.initials: AG
authors.lastname: Algarra
authors.forename: Manuel G
authors.initials: MG
authors.lastname: Basallote
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D061565:Cycloaddition Reaction; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular
chemical_list: D000480:Alkynes
keywords: CS bond formation; activation strain model; density functional calculations; kinetics; reaction mechanisms