Titanium Complexes Stabilized by a Sulfur‐Bridged Chelating Bis(aryloxo) Ligand as Active Catalysts for Olefin Polymerization

The mixed-ligand complexes [Ti2(μ-OR)2(OR)2(κ3-tbop)2] (1a) for R = Me and (1b) R = Et were prepared by the reaction of Ti(OR)4 and H2tbop {H2tbop = 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol]} in methanol. Treatment of 1a and 1b with AlMe3 led to the substitution of terminal alkoxy groups to create the organometallic compounds [Ti2(μ-OR)2(κ3-tbop)2(Me)2] (2a) for R = Me and (2b) for R = Et. Controlled hydrolysis of 2b causes the evolution of methane and the formation of the titanoxane compounds [{Ti2(μ-OEt)2(κ3-tbop)2}2(μ-O)2]·2CH2Cl2 (3). Structures of 1a, 1b, 2a, 2b, and 3 were confirmed by NMR spectroscopy; 1b and 3 were further investigated with X-ray crystallography. Compounds 1a…

Physico-chemical characterization of polyethylenes obtained in the presence of different catalysts containing alkoxyligands

The effect of the kind and number of alkoxy ligands (OR) in organometallic Ti-Al catalyst on the properties of polyethylenes obtained i.e. molecular weight, mechanical and rheological properties, density, crystallinity, melting point, heat of fusion and number of chain branches was studied. Polyethylene obtained over Ti-Al catalyst with OR ligands has particularly high molecular weight, high den­sity, better mechanical properties, higher resistance to heat, different rheological characteristics and lower number ot chain branches in comparison with standard HDPE. It is possible to control the polyethylene synthesis process and to obtain the polymer of required properties by selecting the OR …

DFT analysis of titanium complexes with oxygen-containing bidentate ligands

Strength of the TiO co-ordinate bond in several titanium complexes with bidentate ligands has been investigated by means of DFT. Mutual interaction of particular donors and their influence on Lewis acidity of the central atom have also been studied. The energy of ligand binding ranges from −19 to −454 kJ/mol, depending on the kind of donors. Calculations confirm that a strong donor, alkoxide anion, co-ordinatively saturates the titanium and makes binding of new ligands less exoenergetic. On the contrary, two oxygen atoms of similar donor number do not have much influence on each other. Strength of the TiO bonds in titanium complexes with certain oxygen-containing bidentate ligands has bee…

2-Tetrahydrofurfuroxo-vanadium-(III) and -(IV) complexes. Synthesis, structures and reactivities of [V2Mg2(μ3,δ2-thffo)2(μ,δ2-thffo)4Cl4]· 2CH2Cl2 and [V2(μ,δ2-thffo)2Cl2O2] †

Vanadium complexes of 2-tetrahydrofurfuroxide (2-tetrahydrofurylmethoxide) (thffo) with the metal in oxidation state III and IV have been prepared and characterized. The reaction of [VCl3(thf)3] with 1.5 equivalents of [Mg(thffo)2] in tetrahydrofuran (thf) or CH2Cl2 led to the formation of [V2Mg2(µ3,η2-thffo)2(µ,η2-thffo)4Cl4]· 2CH2Cl21. Its structure consists of centrosymmetric tetranuclear molecules and CH2Cl2 of crystallization. Two Mg and two V atoms have distorted octahedral geometry and form a nearly regular Mg2V2 rhombus. The V · · · V distance is 3.266(2) A. The reaction of [VOCl2(thf)2] with Na(thffo) in thf yielded [V2(µ,η2-thffo)2Cl2O2] 2. Two VOCl units are linked by alkoxide ox…

Zirconium and hafnium complexes of the thio(bisphenolato) ligand: synthesis, structural characterization and testing as 1-hexenepolymerizationcatalysts

Thio(bisphenolato) complexes of the type [M2(mu-tbop-kappa3O,S,O)2Cl4] [M = Zr 1, Hf 2 and tbop = 2,2-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenolate}] were prepared by HCl elimination from tbopH2 and MCl4. Substitution of the chlorides in 1 and 2 by 2,6-diisopropylphenolato groups (dipp) generates new compounds [M2(mu-tbop-kappa3O,S,O)2(dipp)4] (M = Zr 3, Hf 4). The structures of 1-4 were confirmed by NMR spectroscopy; complexes 3 and 4 were further investigated by X-ray crystallography. These studies showed 1-4 to be dimers either in the solid state or in solution and to have metal centers adopting distorted octahedral geometry. However treatment of MCl4 with [Al2(mu-OEt)2(tbop-kappa3O,S,O…

Ziegler–Natta catalysts based on vanadium halides: a DFT study

Abstract Ziegler–Natta ethylene insertion into the carbon–metal bond for a number of fragments containing vanadium on different oxidation states as well as the halogen ligands has been studied by means of DFT. It is shown that the complexation and insertion energies are strongly influenced by the charge on the transition metal atom and, to some extent, by the electronegativity of the halogen atom. Complexation energy varies in the range −129 to −159 kJ/mol for charged species and −64 to −77 kJ/mol for neutral ones. Insertion energy follows a similar pattern and ranges from −28 to −62 and −82 to −100 kJ/mol, respectively. The calculated values are compared with the experimental results and d…

Sulfur Dioxide Oxidation Catalyzed by Photosensitized Ytterbium Diphthalocyanine

Oxidation of SO2 into SO3 was found effectively catalyzed by photosensitized ytterbium diphthalocyanine, YbPc2 (Pc = phthalocyanine ligand, C32H16N8) when performed in air-saturated dimethylformamide (DMF) solution at 20 °C. The process follows according to a multi-step complex mechanism involving chemical induction as its driving force. Excitation energy of the sandwich molecular system in YbPc2 is used to promote the reaction by creating a reactive intermediate form of the ytterbium complex hosting up to eight SO2 molecules. The conversion of SO2 proved complete.

Photocatalytic activity of nano and microcrystalline TiO2 hybrid systems involving phthalocyanine or porphyrin sensitizers

Hybrid photocatalysts based on TiO(2)-anatase matrix, representing the both micro- and nano-structures, impregnated with selected lanthanide diphthalocyanine and metalloporphyrin sensitizers, were compared to evaluate their activity and effectiveness in a water suspension catalytic system designed to degrade 4-nitrophenol (4-NP) in a UV-stimulated reaction. Either type of the anatase catalyst was proved to be effective in mineralizing of 4-NP. However, kinetic studies confirmed that the composite's efficiency basically depends on the nature of the macromolecular sensitizer and to a minor extent on the dimensions (micro/nano) of the TiO(2) particles. The apparent higher activity observed for…

New intermediates for the synthesis of olefin polymerization catalysts: the complexes [M2(µ-Cl)2Cl4(thf)4](M = Ti or V, thf = tetrahydrofuran); Crystal structures and properties

The dimeric titanium(III) and vanadium(III) complexes [M2(µ-Cl)2Cl4(thf)4](M = Ti 1 or V 2, thf = tetrahydrofuran) have been prepared by recrystallization of [MCl3(thf)3] from dichloromethane. In the dimers, composed of slightly distorted edge-sharing octahedra, the metal atoms separated by Ti ⋯ Ti and V ⋯ V distances of 3.711 (3) and 3.619(1)A, respectively, are surrounded by two terminal Cl atoms, two oxygen atoms of thf molecules and are linked by two bridging Cl atoms. The geometry around the titanium atoms differs from that around vanadium because the thf molecules and the terminal chlorine atoms are differently located with respect to the bridging chlorine atoms of the M2(µ-Cl)2 unit.…

Synthesis, structural studies and reactivity of vanadium complexes with tridentate (OSO) ligand

The direct reaction between [VCl(3)(thf)3] or [VO(OEt)3] and 2,2'-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenol (tbopH(2)) leads to the formation of [V(2)(micro-tbop-kappa(3)O,S,O)2Cl(2)(CH(3)CN)(2)] (1).4CH(3)CN or [V(2)(micro-OEt)2(O)2(tbop-kappa(3)O,S,O)2] (2), respectively, in high yield. Compounds 1 and 2 were characterized by chemical and physical techniques including X-ray crystallography and variable temperature magnetic susceptibility studies (J = -29.1 cm(-1)) for 1. Complexes 1 and 2 were supported on MgCl2 and when activated with aluminium alkyls, were found to effectively polymerize ethene to produce polyethylene with a narrow molecular weight distribution M(w)/M(n) approximately…

Syntheses, Structure, and Reactivity of Chiral Titanium Compounds: Procatalysts for Olefin Polymerization

Titanium complexes with chelating alkoxo ligands have been synthesised with the aim to investigate titanium active centres in catalytic ethylene polymerisation. The titanium complexes cis-[TiCl2(η2-maltolato)2] (1, 89 %), and cis-[TiCl2(η2-guaiacolato)2] (2, 80 %) were prepared by direct reaction of TiCl4 with maltol and guaiacol in toluene. The addition of maltol to [Ti(OiPr)4] in THF results in the formation of species [Ti(OiPr)2(maltolato)2] (3, 82 %). The titanium compound cis-[Ti(OEt)2(η2-maltolato)2] (4, 74 %) was obtained by the transesterification reaction of species 3 with CH3CO2Et. When compound 4 is dissolved in THF a dinuclear species [Ti2(μ-OEt)2(OEt)4(η2-maltolato)2] (5, 45 %)…

Synthesis of Ultra-High-Molecular-Weight Polyethylene

The catalytic activity of organometallic Ti-Al complexes with donor ligands in the low-pressure polymerization of ethylene was studied. These complexes were obtained by the reaction of ethylaluminium compounds like AlEt2Cl or Al2Et3Cl3 and titanium compound of the type Ti(OR)nCl4-n (where: R = C2—C10 alkyl, C6H5, C6H4X; X — m-CH3, p-CH3, m-OCH3, p-OCH3, m-Cl, p-Cl, p-Br; n = 1—4). The optimum conditions for the synthesis of these compounds, as well as their physico-chemical properties were studied by means of EPR and polarographic methods. The effect of the type and number of OR ligands in a catalytic system on the yield of polyethylene and on its properties was examined. Ti-Al catalysts wi…

Complexes of Transition Metals with Lewis Bases as Precursors of Olefin Polymerisation Catalysts. 2. Progress in Computer Assisted Design of Catalysts

Titanium Complexes of Chelating, Dianionic O,S,O‐Bisphenolato Ligands: Syntheses, Characterisation, and Catalytic Activity

Titanium complexes based on 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenolato] (tbop) are prepared by reaction of TiCl 4 or Ti(NMe 2 ) 4 with the parent biphenol. Three new complexes are reported: [Ti 2 (μ-tbop-κ 3 O,S,O)(μ-tbop-κ 2 O,O)-(tbop-κ 3 O,S,O)Cl 2 ] (1).2CH 3 CN, [Ti 2 (μ-tbop-κ 3 O,S,O) 2 Cl 4 ] (2) and [Ti(tbop-κ 3 O,S,O) 2 ] (3). Substitution of the chlorides in 1 and 2 by 2,6-diisopropylphenolato and imido (NtBu) ligands generates the new compounds [Ti 2 (μ-tbop-κ 3 O,S,O) 2 -Cl 2 (dipp) 2 ] (4).Et 2 O and [Ti 2 (μ-tbop-κ 3 O,S,O) 2 (NtBu) 2 -(NH 2 tBu) 2 ] (5), respectively. Treatment of 5 with crude Me 3 -SiCl, containing Me 3 SiOH, produces [Ti(tbop-κ 3 O,S,O)Cl(O-SiMe 3 …