Polymerization of propene and 1,3-butadiene with Vanadyl(V) monoamidinate precatalysts and MAO or dialkylaluminum chloride cocatalysts

Two new vanadyl(V) amidinates have been synthesized and characterized by single crystal X-ray diffraction and H-1 NMR. The complexes are dimeric with Cl bridges and monodentate coordination of the amidinate ligand to pseudooctahedral vanadium. In the presence of organometallic compounds of aluminum, these vanadyl complexes promote polymerization of propene and 1,3-butadiene

Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition-Metal Compounds: A Theoretical Study

The nature of intermolecular interactions governing supramolecular polymerizations is very important to control their cooperativity. In order to address this problem, supramolecular columns made of Pt(II) and Pd(II) complexes of oligo(phenyleneethynylene)-based pyridine (OPE) and tetrazolyl-pyridine ligands (TEP) were investigated through the dispersion-corrected PM6 method. Aromatic, CH-π, M-Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of Pt(II) have led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor to control cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger pre-formed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons