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β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands

Opened Access β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands

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Autor: Martínez Prieto, Luis Miguel
Ávila, Elena
Palma, Pilar
Álvarez González, Eleuterio
Cámpora, Juan
Fecha: 2015
Publicado en: Chemistry - a European Journal, 21 (27), 9833-9849.
Tipo de documento: Artículo
Resumen: Nickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of [((iPr)PCP)Ni-OMe] affords polynuclear carbonyl phosphine complexes. Both decomposition processes are initiated by β-hydrogen elimination (BHE), but the resulting [((iPr)PCP)M-H] hydrides undergo divergent reaction sequences that ultimately lead to the irreversible breakdown of the pincer units. Whereas the Pd hydride spontaneously experiences reductive C-H coupling, the decay of its Ni analogue is brought about by its reaction with formaldehyde released in the BHE step. Kinetic measurements showed that the BHE reaction is reversible and less favourable for Ni than for Pd for both kinetic and thermodynamic reasons. DFT calculations confirmed the main...
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Cita: Martínez Prieto, L.M., Ávila, E., Palma, P., Álvarez González, E. y Cámpora, J. (2015). β-Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands. Chemistry - a European Journal, 21 (27), 9833-9849.
Tamaño: 2.555Mb
Formato: PDF

URI: http://hdl.handle.net/11441/65616

DOI: 10.1002/chem.201500652

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