Journal of Organometallic Chemistry p. 123 - 131 (1996)
Update date:2022-08-18
Topics:
Kapteijn, Gerardus M.
Dervisi, Athanasia
Verhoef, Michel J.
Van Den Broek, M.A. Frederik H.
Grove, David M.
Van Koten, Gerard
Reaction of N-ligated methylpalladium(II) alkoxide and aryloxide complexes [Pd(Me)(OR)(N ~ N)] (R = Ph, CH(CF3)2; N ~ N = tmeda (N,N,N′,N′-tetramethylethylenediamine) or bpy (2,2′-bipyridyl)) with carbon monoxide produces the corresponding methylesters in high yields. The insertion takes place either into the Pd-Me bond (aryloxide complexes) or into the Pd-OR bond (alkoxide complexes). Methylpalladium(II) methoxide complexes [Pd(Me)(OMe)(N ~ N)] (N ~ N = tmeda, bpy) have been generated in situ by aryloxide- or alkoxide-methanol exchange reactions for which the equilibrium constants have been determined. The bpy-ligated methylpalladium methoxide complex undergoes insertion of CO producing either a methylpalladium methoxycarbonyl complex [Pd(Me)(CO2Me)(bpy)] (at -60°C) or an acylpalladium methoxycarbonyl complex [Pd(COMe)(CO2Me)(bpy)] (at -25°C); both carbonylated species could be isolated and characterized at low temperature.
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