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Mechanism for Hydride-Assisted Rearrangement from Ethylidene to Ethylene in Iridium Cationic Complexes

AuthorsBesora, María; Vyboishchikov, Sergei F.; Lledós, Agustí; Maseras, Feliu; Carmona, Ernesto ; López Poveda, Manuel
Hydride alkylidene complexes
Alkyl ligands
Issue Date14-Apr-2010
PublisherAmerican Chemical Society
CitationOrganometallics 29(9): 2040-2045 (2010)
AbstractThe cationic hydride alkylidene complexes [TpMe2Ir(═CH−CH3)(H)(PMe3)]+ and [Cp*Ir(═CH−CH3)(H)(PMe3)]+ (TpMe2 = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; Cp* = pentamethylcyclopentadienyl) are experimentally known to tautomerize to the corresponding hydride alkene species. Our computational study on the mechanism shows that the reaction takes place through formation of the corresponding alkyl intermediates, with participation of species involving α- and β-CH agostic interactions. Computed energy barriers reproduce the available experimental kinetic data and agree with a much faster process in the Cp* system. The highest stabilization of the hydride alkylidene complex (the reactant) in the TpMe2 system appears as the main reason for the higher barrier found. The difference between the two complexes is due to the steric effects of the spectator ligands.
Description6 páginas, 3 figuras, 5 esquemas.
Publisher version (URL)http://dx.doi.org/10.1021/om1000315
Appears in Collections:(IIQ) Artículos
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