1345470-92-9Relevant academic research and scientific papers
Facile synthesis and reactivity study of mixed phosphane-isocyanide Pd(II) and Pd(0) complexes
Canovese, Luciano,Visentin, Fabiano,Levi, Carlo,Santo, Claudio,Bertolasi, Valerio
, p. 239 - 249 (2011)
The reaction between an equimolecular mixture of isocyanide CNR (CNR = di-methylphenyl isocyanide (DIC), tert-butyl isocyanide (TIC), triphenyl phosphane (PPh3) and a dechlorinated solution of the palladium allyl dimers [Pd(η3-allyl)Cl]2 (allyl = 2-Meallyl, 1,1-Me2allyl) in stoichiometric ratio yields the mixed derivative [Pd(η3-allyl)(CNR)(PPh3)] only. Apparently, the mixed derivative represents the most stable species among all the possible ones that might be formed under those experimental conditions. Theoretical calculations are in agreement with the experimental observation and the energy stabilization of the mixed species with respect to the homoleptic derivatives is traced back to an overall push-pull effect exerted by the isocyanide and the phosphane acting synergically. Similar behavior is observed in the case of the synthesis of the palladacyclopentadienyl complexes [Pd(C4(COOMe) 4)(CNR)(PPh3)] and of the palladium(0) olefin complexes whose synthesis invariably yields the mixed [Pd(η2-olefin)(CNR) (PPh3)] derivatives. The paper includes studies on the reactivity toward allylamination in the case of the palladium(II) allyl complexes. A diffractometric investigation on the solid state structures of four different palladium isocyanide-phosphane complexes is also included.
