ChemInform Abstract: Homogeneous Catalysis with Dicationic Pd(II) Complexes: Aldol Reaction of Methyl Isocyanoacetate with Benzaldehyde.

Abstract

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Chiral, Hemilabile Palladium(II) Complexes of Tridentate Oxazolidines, IncludingC2-Symmetric “Pincers”

“…Structural comparison of the cations of 8 maj (disorder removed for clarity) and a representative Pd(II)-pybox complex . The ball-and-stick models are oriented such that the coordination plane of the metal is perpendicular to the page, and the ligand trans to the pyridyl donor points toward the reader.…”

“…The N ox −Pd−N py angles were less than 90 ° (83.50(11)° and 84.19(11)°) on account of steric requirements of the ligand, while the N ox −Pd−Cl angles were greater (95.53(9)° and 96.84(8)°). All of these characteristics were held in common with the known structures of analogous Pd(II)-pybox derivatives . However, the latter were essentially planar except for their C 4 -substituents that projected above and below the plane defined by the metal and the ligand, whereas the oxazoldinyl rings in 8 maj were substantially buckled.…”

“…However, the latter were essentially planar except for their C 4 -substituents that projected above and below the plane defined by the metal and the ligand, whereas the oxazoldinyl rings in 8 maj were substantially buckled. Figure shows a side-by-side comparison of the structures of the cations of 8 maj and a representative Pd(II)-pybox complex . In contrast to the oxazoline complex, the metal center in 8 maj was crowded above and below the coordination plane by the methyl groups at the C 4 -positions of the oxazolidine rings.…”