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http://hdl.handle.net/2445/168261
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 Lligands Chemical kinetics Ligands |
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: https://doi.org/10.1039/c4dt01463d |
It is part of: | Dalton Transactions, 2014, vol. 43, num. 36, p. 13525-13536 |
URI: | http://hdl.handle.net/2445/168261 |
Related resource: | https://doi.org/10.1039/c4dt01463d |
ISSN: | 1477-9226 |
Appears in Collections: | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
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