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Title: Kinetico-mechanistic study on the C-H bond activation of primary benzylamines; cooperative and solid-state cyclopalladation on dimeric complexesss
Author: Font, H.
Font Bardia, Ma. Mercedes
Gómez, K.
González, G.
Granell Sanvicente, Jaime Ramón
Macho, I.
Martínez López, Manuel, 1957-
Keywords: Cinètica química
Chemical kinetics
Issue Date: Sep-2014
Publisher: Royal Society of Chemistry
Abstract: The cyclometallation reactions of dinuclear μ-acetato complexes of the type [Pd(AcO)(μ-AcO)L]2 (L = 4-RC6H4CH2NH2, R = H, Cl, F, CF3), a process found to occur readily even in the solid state, have been studied from a kinetico-mechanistic perspective. Data indicate that the dinuclear acetato bridged derivatives are excellent starting materials to activate carbon-hydrogen bonds in a facile way. In all cases the established concerted ambiphilic proton abstraction by a coordinated acetato ligand has been proved. The metallation has also been found to occur in a cooperative manner, with the metallation of the first palladium unit of the dimeric complex being rate determining; no intermediate mono-metallated compounds are observed in any of the processes. The kinetically favoured bis-cyclopalladated compound obtained after complete C-H bond activation does not correspond to the final isolated XRD-characterized complexes. This species, bearing the classical open-book dimeric form, has a much more complex structure than the final isolated compound, with different types of acetato ligands
Note: Versió postprint del document publicat a:
It is part of: Dalton Transactions, 2014, vol. 43, num. 36, p. 13525-13536
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ISSN: 1477-9226
Appears in Collections:Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)

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