12129-06-5Relevant articles and documents
TRI-1-METHALLYL- AND 1-METHALLYL-BUTADIENE GROUP IV TRANSITION METAL COMPLEXES
Blenkers, J.,Meijer, H. J. de Liefde,Teuben, J. H.
, p. 383 - 394 (1981)
Reaction of Cp'MCl3 (Cp' = η5-C5(CH3)5; M = Ti, Zr, Hf) with 2-butenylmagnesium bromide at low temperatures gives Cp'M(1-methallyl)3, which is readily converted into Cp'M(η3-1-methallyl)(η4-butadiene) on heating.Only Cp'Hf(1-methallyl)3 could be isolated; it is fluxional and its NMR and IR spectra indicate that it consists of a complex mixture of isomers containing interconverting η1- and η3-1-methallyl groups.The compounds Cp'M(η3-C4H7)(η4-C4H6) are much more thermally stable; they show fluxional behaviour, but this is limited to theη3-1-methallyl group.These complexes are very reactive towards a large variety of organic substrates.
Reactivity of functionalised decamethyltitanocenes: Synthesis and structure of chiral monocyclopentadienyl titanium halogenides
Burlakov, Vladimir V.,Lyssenko, Konstantin A.,Spannenberg, Anke,Baumann, Wolfgang,Arndt, Perdita,Shur, Vladimir B.,Rosenthal, Uwe
, p. 76 - 80 (2013)
The recently described unconventional substituted titanocene complex [Cpa -Ti{η5-C5Me3(CH 2-CH(tBu)-η2-C2-CH(tBu)-CH2)}] (1) can be derivatised by simple means (Br2, HX with X = Cl, Br) to generate the titanocene dihalogenides 2-Br, 2-Cl, which give in a subsequent reaction besides Cpa&-TiX3 (3-Br: X = Br, 3-Cl: X = Cl) the titanium complexes 4-Cl resp. 4-Br with one functionalised chiral cyclopentadienyl ligand. In the reaction of 1 with Et3N·3HF an analogous isostructural titanocene dihalogenide 2-F as well as the unusual dimeric anionic heptafluoride 5 are formed. All complexes have been characterised spectroscopically, and X-ray crystal structure determinations were performed for 4-Cl and 2-F.
Reactions of Organotitanoxane Fluorides with AlR3 (R = Me, Et, CH2Ph) and Me3SiCl: X-ray Crystal Structures of [C5Me5Ti(μ-O)]4F[(μ-F)AlMe 3]3, [C5Me5Ti(μ-O)]4F 3[(μ-F)Al(CH2Ph)3]
Yu, Peihua,Pape, Thomas,Uson, Isabel,Said, Musa A.,Roesky, Herbert W.,Montero, Mavis L.,Schmidt, Hans-Georg,Demsar, Alojz
, p. 5117 - 5124 (1998)
A new pentamethylcyclopentadienyl titanoxane fluoride (C5Me5)4Ti4O5F 2 (1b) has been synthesized from (C5-Me5)4Ti4O5Cl 2 using the fluorinating reagent Me3SnF. The fluorination of organotitanoxane chlorides proceeds via a proposed intermediate similar to the four-membered ring Ti(μ-Cl)(μ-F)Sn and the bridged Ti(μ-F)ClSnMe3 species. The reactions of 1b and [C5Me5Ti(μ-O)F]4 with AlR3 (R = Me, Et, CH2Ph) afforded the thermally unstable adducts [C5Me5Ti(μ-O)]4F 4-n[(μ-F)AlR3]n (n = 1-4), which proceed with selective exchange of fluorine atoms for alkyl groups to give an eight-membered alkylated ring compound [C5Me5Ti(μ-O)R]4. The reactions of 1b and [C5Me5Ti(μ-O)F]4 with Me3SiCl result in exchange of fluorine for chlorine atoms. Moreover, using an excess of Me3SiCl leads to a novel oxygen-chlorine exchange reaction to give C5Me5Ti(μ-O)]4F[(μ-F)AlMe 3]3 . The crystal structures of complexes (C5Me5)4Ti4O5X 2 (X = Cl (1a), F (1b)), [C5Me5Ti(μ-O)]4F[(μ-F)AlMe 3]3 (2b), [C5Me5Ti(μ-O)]4F 3[(μ-F)Al(CH2Ph)3] (3a), and [C5Me5Ti(μ-O)Et]4 (4) have been determined by X-ray diffraction studies, Both chlorides and fluorides in 1a and Ib, respectively, are oriented to the exo position of their butterfly structures. The bond lengths of the terminal fluorines (Ti-Ft) in compounds 2b and 3a are discussed with respect to the deviation from the bond lengths of the bridging fluorines (Ti-Fb-Al). The structure of 4 displays a nonplanar Ti4O4 ring conformation as shown in 2b and 3a.
Influence of ligands and cocatalyst on the activity in ethylene polymerization of soluble titanium complexes
Conti, Giuseppe,Arribas, Guillermo,Altomare, Angelina,Ciardelli, Francesco
, p. 41 - 50 (1994)
Known and new titanium complexes bearing alkoxy, phenoxy, carboxylate and cyclopentadienyl ligands in addition to chlorine have been tested towards ethylene polymerization after activation with aluminum alkyls (AlR3) or methylalumoxane (MAO). In the absence of cyclopentadienyl ligands the optimal productivity obtained is very similar either with AlR3 or MAO, but higher MAO/Ti than AlR3/Ti ratios are necessary. In the case of complexes with the Cp ligand much better productivity can be obtained with high MAO ratios thus confirming that under these conditions a different activation mechanism is operative.
Highly efficient one-step direct synthesis of monocyclopentadienyltitanium complexes
Zhang, Yuetao,Mu, Ying
, p. 631 - 634 (2008/10/09)
This report describes a highly efficient one-step synthetic strategy for monocyclopentadienyltitanium complexes by the direct reaction of TiCl 4 with substituted cyclopentadienes, without adding any other reagents. This new synthetic method is particularly efficient for cyclopentadienes with a pendant group that can bond or coordinate to the Ti atom.
