Binuclear and multinuclear complexes have attracted much attention due to their unique catalytic performances for olefin polymerization compared with their mononuclear counterparts. In this work, a series of phenyl-bridged bis-β-carbonylenamine [O⁻NS^R] (R = alkyl or phenyl) tridentate ligands and their binuclear titanium complexes (Ti²L₁–Ti²L₅) were synthesized and characterized by ¹H NMR, ¹³C NMR, FTIR and elemental analysis. The molecular structure of ligand L₂ (R = ⁿPr) and its corresponding Ti complex Ti²L₂ were further investigated by single-crystal X-ray diffraction, which showed that each titanium coordinated with six atoms to form a distorted octahedral configuration along with the conversion of the ligand from β-carbonylenamine to β-imino enol form. Under the activation of MMAO, these complexes catalyzed ethylene polymerization and ethylene/α-olefin copolymerization with extremely high activity (over 10⁶ g mol (Ti)⁻¹ h⁻¹ atm⁻¹) to produce high molecular weight polyethylene. At the same time, wider polydispersity as compared with the mononuclear counterpart TiL₆ was observed, indicating that two active catalytic centers may be present, consistent with the asymmetrical crystal structure of the binuclear titanium complex. Furthermore, these complexes possessed better thermal stability than their mononuclear analogues. Compared with the complexes bearing alkylthio sidearms, the complex Ti²L₅ bearing a phenylthio sidearm exhibited higher catalytic activity towards ethylene polymerization and produced polyethylene with much higher molecular weight, but with an appreciably lower 1-hexene incorporation ratio. Nevertheless, these bis-β-carbonylenamine-derived binuclear titanium complexes showed much higher ethylene/1-hexene copolymerization activity and 1-hexene incorporation ratios as compared with the methylene-bridged bis-salicylaldiminato binuclear titanium complexes, and the molecular weight and 1-hexene incorporation ratio could be flexibly tuned by the initial feed of α-olefin commoners and catalyst structures.

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature ¹³C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 10⁶ g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti²L₁ with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.