191110-41-5Relevant academic research and scientific papers
Structural insight into (2-Oxy-π-allyl)palladium and -platinum complexes as precursors of oxodimethylenemethane complexes
Ohsuka, Akihiro,Wardhana, Tjandra W.,Kurosawa, Hideo,Ikeda, Isao
, p. 3038 - 3043 (1997)
X-ray crystallographic structures of η3-allylpalladium and -platinum complexes bearing an acetal group at the 2-position {[M(η3-CH2C(OCH2OCH3)CH 2)(PPh3)2](PF6) (M = Pd (1a), Pt (1b)) and [M(η3-CH2C(O-2-C5H9O)CH 2)(PPh3)2](PF6) (M = pd (2a), Pt (2b))}) reveal that they have a large contribution of oxonium structure, regardless of the kind of metal. Depending on the structure of the acetal moiety, these η3-allyl complexes show different reactivities toward hydroxide and methoxide ion as nucleophiles. The generation mechanism of oxodimethylenemethane complexes {[M(η3-CH2C(O)CH2)(PPh3) 2](PF6) (M = Pd (3a), Pt (3b))} from these acetal compounds was discussed on the basis of the X-ray crystallographic structures, the analysis of reaction products, and the 18O isotope-labeling technique. Nucleophilic displacement at the 2-position of η3-allylpalladium complexes was directly proved for the first time by the isotope technique.
