NDLI: Mechanism of [3+2] Cycloaddition of Alkynes to the $[Mo_{3}S_{4}(acac)_{3}(py)_{3}][PF_{6}]$ $Cluster^{†}$

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Mechanism of [3+2] Cycloaddition of Alkynes to the $[Mo_{3}S_{4}(acac)_{3}(py)_{3}][PF_{6}]$ $Cluster^{†}$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Algarra, Andrés G. Hernández-molina, Rita Pino-chamorro, Jose Ángel Gushchin, Artem L. Fernández-trujillo, M. Jesús Vicent, Cristian Basallote, Manuel G.
Description	Author Affiliation: Pino-Chamorro JÁ ( 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.)
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 $[Mo_{3}S_{4}(acac)_{3}(py)_{3}][PF_{6}]$ $([1]PF_{6};$ acac=acetylacetonate, py=pyridine) with two RCCR alkynes $(R=CH_{2}OH$ (btd), COOH (adc)) in $CH_{3}CN.$ 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.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	7
Volume Number	21
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2015-02-09
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Alkynes Chemistry Magnetic Resonance Spectroscopy Cycloaddition Reaction Kinetics Models, Molecular Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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