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…
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…
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 %)…
Homo- and Heterometallic Aluminum and Titanium Complexes of Tridentate (OSO) Ligand: Synthesis, Structure, and Catalytic Activity
The tridentate (OSO-functions) biphenol, 2,2‘-thiobis{4-(1,1,3,3-tetramethylbutyl)phenol} (tbopH2), reacts with AlMe3 to give [Al2(μ-tbop-κ3O,S,O)2Me2] (1). Alcoholysis of 1 results in the formation of [Al2(μ-OEt)2(tbop-κ3O,S,O)2] (2). The reaction of 2 with TiCl4 gives the trimeric complex [Ti3(μ-OEt)2(μ-tbop-κ3O,S,O)2Cl6] (3)·C6H14. Alkylation of 3·C6H14 with LiMe produces two dimeric complexes, [Ti2(μ-tbop-κ3O,S,O)2Me4] (4) and [Ti2(μ-OE)2(tbop-κ3O,S,O)2Me2] (5)·Et2O. Treatment of [Ti2(μ-OEt)2(tbop-κ3O,S,O)2(OEt)2] with AlMe3 and EtOH afforded the heterobimetallic species, [Ti2Al2(μ-OEt)6(μ-tbop-κ3O,S,O)2(OEt)4] (6). The structures of 1−6 were confirmed by NMR spectroscopy; complexes 1, …
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 …