Decomposition of Methylnickel(II) Amido, Alkoxo, and Alkyl Complexes by β-Hydrogen Elimination: A Comparative Study

descriptionPublicationkeyboard_double_arrow_right Article 28 Oct 2009 English Publisher:American Chemical Society (ACS)Journal:Organometallics, volume 28, pages 6,515-6,523 (issn: 0276-7333, eissn: 1520-6041,

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Authors: Matas, Inmaculada; Cámpora, Juan; Palma, Pilar; Álvarez, Eleuterio;

doi: 10.1021/om900400s

handle: 10261/37705

Decomposition of Methylnickel(II) Amido, Alkoxo, and Alkyl Complexes by β-Hydrogen Elimination: A Comparative Study

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Abstract

Thermal decomposition of structurally related amido, alkoxo, and alkyl complexes of type [Ni(Me)(EC(H)RR′)(dippe)] (EC(H)RR′ = cyclo-NC4H8 (pyrrolidino), N(CH2Ph)2, OCH2Ph, OCH(Me)Ph, and CH2CH2Ph) takes place through formally analogous processes involving β-hydrogen elimination and reductive elimination of methane, cleanly affording corresponding Ni(0) imine, aldehyde, ketone, and olefin complexes, [Ni(η2-E═CRR′)(dippe)]. Kinetic studies on these decomposition reactions show that, in spite of their similarity, they involve substantial mechanistic differences.

Financial support from the DGI (Project CTQ2006-05527/BQU) and Junta de Andalucía (Project P06-FQM-01704) is gratefully acknowledged

9 páginas, 7 figuras, 6 esquemas.

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Keywords

β-hydrogen, Methylnickel, Alkoxo, Amido, Thermolysis, Methane, Alkyl

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