Zinc 2-((2-(benzoimidazol-2-yl)quinolin-8-ylimino)methyl)phenolates : synthesis, characterization and photoluminescence behavior

A series of 2-(2-(1H-benzoimidazol-2-yl)quinolin-8-yliminomethyl)phenol derivatives and their zinc complexes (C1 – C5) were synthesized and fully characterized. The molecular structure of the representative complex C2 was determined by single crystal X-ray diffraction, which revealed that the zinc was five-coordinated with the tetra-dentate ligand and a methanol bound to the metal afford a distorted square-pyramidal geometry. The UV-Vis absorption and fluorescence spectra of the organic compounds and their zinc complexes were measured and investigated in various solvents such as methanol, THF, dichloromethane, and toluene; significant influences by solvents were observed on their luminescent properties; red-shifts for the zinc complexes were clearly observed in comparisons to the free organic compounds

Recent progress on nickel-based systems for ethylene oligo-/polymerization catalysis

Recent progress on nickel-based complex pre-catalysts is reviewed herein. The ethylene oligo-/polymerization behaviour is discussed in terms of the variation of the complex models bearing different kinds of ligand sets. These discussions focus mainly on the influence that the different substituents present have on the observed catalytic activity, the results of which can guide the design of new target structures possessing high ethylene activity

Synthesis and characterization of 2-(2-benzhydrylnaphthyliminomethyl)pyridylnickel halides: formation of branched polyethylene

A series of 2-(2-benzhydrylnaphthyliminomethyl)pyridine derivatives (L1–L3) was prepared and used to synthesize the corresponding bis-ligated nickel(II) halide complexes (Ni1–Ni6) in good yield. The molecular structures of representative complexes, namely the bromide Ni3 and the chloride complex Ni6, were confirmed by single crystal X-ray diffraction, and revealed a distorted octahedral geometry at nickel. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all nickel complex pre-catalysts exhibited high activities (up to 2.02 × 10⁷ g(PE) mol⁻¹(Ni) h⁻¹) towards ethylene polymerization, producing branched polyethylene of low molecular weight and narrow polydispersity. The influence of the reaction parameters and the nature of the ligands on the catalytic behavior of the title nickel complexes were investigated

Dialkylaluminium 2-imidazolylphenolates: Synthesis, characterization and ring-opening polymerization behavior towards lactides

The stoichiometric reaction of the 2-imidazolylphenols (L1–L9) with the trialkylaluminium reagents AlR₃ (R = Me, Et and iBu), afforded the corresponding dialkylaluminium 2-imidazolylphenolate complexes [R₂Al(L1–L9)] (C1–C11), which were characterized by ¹H/¹³C NMR spectroscopy and by elemental analysis. The molecular structures of the representative complexes C1, C2, C4, C6 and C11 were determined by single-crystal X-Ray diffraction, and revealed a distorted tetrahedral geometry at aluminum. These dialkylaluminium 2-imidazolylphenolates (C1–C11) could efficiently catalyze the ring-opening polymerization of lactides to afford high molecular weight polylactide, both in the presence and absence of BnOH, and as such represent rare examples of the use of bi-dentate ligation at aluminum in such lactide polymerization systems. On the basis of the polymerization results for l-lactide, d-lactide and rac-lactide, the nature of the ligands and the aluminum bound alkyls were found to significantly affect the catalytic activity as well as the properties of the resultant polylactides

Dichloropalladium complexes ligated by 4,5-bis(arylimino)pyrenylidenes: Synthesis, characterization, and catalytic behavior towards Heck-reaction

A series of 4,5-bis(arylimino)pyrenylidenylpalladium(II) chloride complexes (C1–C4) were synthesized and characterized by FT-IR and NMR spectroscopy, elemental analysis as well as by single crystal X-ray diffraction for the representative complexes C1 and C3, which revealed a square planar geometry at the palladium center. All palladium complexes exhibited high activity for the Heck cross-coupling reaction, which were effective when conducted in various solvents. Furthermore, the in-situ mixture of palladium dichloride and the ligand (L1) provided an effective catalytic system for the Heck-reaction

Synthesis, characterization and ethylene polymerization behaviour of binuclear nickel halides bearing 4,5,9,10-tetra(arylimino)pyrenylidenes

Pyrene-4,5,9,10-tetraone was prepared via the oxidation of pyrene, and reacted with various anilines to afford a series of 4,5,9,10-tetra(arylimino)pyrenylidene derivatives (L1–L4). The tetraimino-pyrene compounds L1 and L2 were reacted with two equivalents of (DME)NiBr₂ in CH₂Cl₂ to afford the corresponding dinickel bromide complexes (Ni1 and Ni2). The organic compounds were fully characterized, whilst the bi-metallic complexes were characterized by FT-IR spectra and elemental analysis. The molecular structures of representative organic and nickel compounds were confirmed by single-crystal X-ray diffraction studies. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me₂AlCl, maintaining a high activity over a prolonged period (longer than previously reported dinickel complex pre-catalysts). The polyethylene obtained was characterized by GPC, DSC and FT-IR spectroscopy and was found to possess branched features

2-{2,6-Bis[bis(4-fluorophenyl)methyl]-4-chlorophenylimino} -3-aryliminobutylnickel(II) bromide complexes: Synthesis, characterization, and investigation of their catalytic behavior

The series of 2-{2,6-bis[di(4-fluorophenyl)methyl]-4-chlorophenylimino}-3- aryliminobutane derivatives (L1-L5) and their nickel(II) dibromide complexes (Ni1-Ni5) were synthesized, and all organic compounds were fully characterized by the Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy and by elemental analysis, while the nickel complexes were characterized by FT-IR spectroscopy, elemental analysis, as well as by single-crystal X-ray diffraction for two representative examples, namely Ni1 and Ni4. A distorted tetrahedral geometry was observed for these four-coordinate nickel complexes. Upon the activation with either Methylaluminoxane or modified methylaluminoxane as co-catalyst, all nickel complex precatalysts showed very high activity toward ethylene polymerization with activities of up to 10 7 g(PE)·mol -1 (Ni)·h -1 , and afforded highly branched polyethylene with a bimodal distribution. © 2014 Elsevier B.V

Half-titanocene 5-t-butyl-2-(1-(arylimino)methyl)quinolin-8-olate chlorides: Synthesis, characterization and ethylene (co-) polymerization behavior

A series of half-titanocene chloride complexes bearing 5-t-butyl-2-(1-(arylimino)methyl)quinolin-8-olate ligands (L), CpTiLCl₂, has been synthesized in acceptable yields by the stoichiometric reaction of CpTiCl₃ with the respective potassium 5-t-butyl-2-(1-(arylimino)methyl)quinolin-8-olate. All half-titanocene complexes were fully characterized by elemental analysis and NMR spectroscopy, and the molecular structures of the representative complexes C1 and C2 were confirmed as pseudo octahedral at titanium by single-crystal X-ray diffraction. When activated with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all titanium complexes exhibited good activities (up to 4.8 × 10⁵ g mol⁻¹(Ti) h⁻¹) towards ethylene polymerization. The obtained polyethylene exhibited ultra-high molecular weight (up to 11.82 × 10⁵ g mol⁻¹) with narrow polydispersity. Furthermore, effective co-polymerization of ethylene with 1-hexene or 1-octene was achieved with several percentages of co-monomer incorporation in the resultant polyethylenes