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A new cationic palladium complex [Pd(η5-C5H5)(PPh2Cy)2]BF4 (I) is prepared by the reaction of [Pd(acac)(PCyPh2)2]BF4 with cyclopentadiene in the presence of BF3·OEt2. The structure of complex I is determined by XRD. Results of the DFT studies at the BP86-D3/def2-TZVP level of theory along with QTAIM and NOCV methods suggest that the hapticity of the cyclopentadienyl ligand in I adopts an intermediate type of coordination between η3 and η5. Compound I demonstrates a catalytic activity in the reaction of 1,3-butadiene telomerization with methanol with a catalyst turnover number up to 43100 (mol·BD)/(mol·Pd) for 6 h and a 76% selectivity to telomeres. [ABSTRACT FROM AUTHOR]

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]