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Synthesis and Reactivity of Nickel an Palladium Fluoride Complexes with PCP Pincer Ligands. A NMR-Based Assessment of Electron-Donating Properties of Fluoride and Other Monoanionic Ligands

Opened Access Synthesis and Reactivity of Nickel an Palladium Fluoride Complexes with PCP Pincer Ligands. A NMR-Based Assessment of Electron-Donating Properties of Fluoride and Other Monoanionic Ligands

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Autor: Martínez Prieto, Luis Miguel
Melero Jiménez, Cristóbal
Rio Díaz-Jara, Diego del
Cámpora Pérez, Juan
Álvarez González, Eleuterio
Fecha: 2012
Publicado en: Organometallics, 31 (4), 1425-1438.
Tipo de documento: Artículo
Resumen: A series of complexes of the type [(iPrPCP)M-L] (M = Ni, Pd), containing the 2,6-bis(diisopropylphosphinomethyl)phenyl (iPrPCP) pincer ligand and simple monoanionic ligands L (F, Cl, Br, H, Me, Ph, NO3, and OTf), have been synthesized and characterized. The fluoride derivatives [(iPrPCP)M-F] were prepared from the halides [(iPrPCP)M-X] (M = Ni, X = Br; M = Pd, X = I) by exchange reactions with AgF or, alternatively, by protonolysis of the methyl complexes [(iPrPCP)M-Me] with Et3N·3HF (TREAT-HF). A survey of the 13C NMR data for the new complexes and previously reported ones with L = OH, OMe, and NH2 revealed significant trends that can be directly related to the electronic properties of the anionic ligands L coordinated to Ni(II) and Pd(II) centers. The chemical shift of the 13C resonance of the metal-bound ipso carbon is very sensitive to the σ-donating capacity of L, which increases in the order L = OTf > NO3 > F > OAc > OMe > Cl > OH ≈ Br > I > NH2 > Ph > Me > H. In addition, the r...
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Cita: Martínez Prieto, L.M., Melero Jiménez, C., Rio Díaz-Jara, D.d., Cámpora Pérez, J. y Álvarez González, E. (2012). Synthesis and Reactivity of Nickel an Palladium Fluoride Complexes with PCP Pincer Ligands. A NMR-Based Assessment of Electron-Donating Properties of Fluoride and Other Monoanionic Ligands. Organometallics, 31 (4), 1425-1438.
Tamaño: 916.5Kb
Formato: PDF

URI: https://hdl.handle.net/11441/79354

DOI: 10.1021/om2009793

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