STRUCTURE AND CATALYTIC PROPERTIES OF PALLADIUM(II) (ACETYLACETONATO- κ2O,O′)BIS(TRIS(DIETHYLAMINO)PHOSPHINE) TETRAFLUOROBORATE.

The structure of complex [Pd(acac){P(NEt2)3}2]BF4 (I) is determined by XRD. In the crystal structure of I, the coordination sphere of palladium is characterized by a significantly distorted planar-square geometry of the central atom. Steric hindrance of the P(NEt2)3 ligand is determined using the XRD and DFT data (the Tolman cone angle is 170-175°). It is established that the pair of P(NEt2)3 ligands in the coordination sphere of palladium is represented by two isomers differing by the geometries (planar and pyramidal) of the nitrogen atom environment. DFT calculations at the BP86/def2-TZVP level of theory suggest that the difference between the substituent geometries in the ligands is due to steric hindrances. In combination with BF3·OEt2, compound I demonstrates catalytic activity in the addition polymerization of norbornene whose average activity reaches 3.6·105 g(NB)/(mol(Pd)·h) at 100 °C. [ABSTRACT FROM AUTHOR]