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 degrees). 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 center dot OEt2, compound I demonstrates catalytic activity in the addition polymerization of norbornene whose average activity reaches 3.6 center dot 10(5) g((NB))/(mol((Pd))center dot h) at 100 degrees C.

Automated summary

The structure of complex [Pd(acac){P(NEt2)(3)}(2)]BF4 (I) and the steric hindrance of P(NEt2)(3) ligand were determined using XRD and DFT data. It was found that the coordination sphere of palladium contains two isomers of P(NEt2)(3) ligands with different geometries due to steric hindrance. Additionally, compound I showed catalytic activity in the addition polymerization of norbornene.