0000000000384855
AUTHOR
Marta E. G. Mosquera
Synthesis and structural characterization of novel tetranuclear organotitanoxane derivatives.
Synthesis of the novel titanoxane compounds, [(TiCl)(TiOH){(Ti)[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](2)(μ-O)}(2)(μ-O)] (4) and [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(4)] (5) by controlled reaction of the dinuclear titanium oxo complex [{Ti{μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)}Cl](2)(μ-O)] (1) with 2 equiv of LiOH is reported. Complex 4 is innovative and remarkable. It is one of the rare known examples of tetranuclear stable terminal hydroxo titanium complexes, with an open-chained structure, which coincides with the transient metal monohydroxo proposed in the stepwise pathway employed to justify the formation of the hexanuclear complex [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(6)] (3) from 1. (1)H DO…
Early transition metal derivatives stabilised by the phenylenediamido 1,2-C6H4(NCH2tBu)2 ligand: Synthesis, characterisation and reactivity studies: Crystal structures of [Ta{1,2-C6H4(NCH2tBu)2}2Cl] and [Zr{(1,2-C6H4(NCH2tBu)2}(NMe2)(μ-NMe2)]2
Abstract Li 2 [1,2-C 6 H 4 (NCH 2 t Bu) 2 ] reacts with one equiv of [TiCl 4 (THF) 2 ] in refluxing toluene to give the chelate compound [Ti{1,2-C 6 H 4 (NCH 2 t Bu) 2 }Cl 2 (THF)] ( 1 ), isolated as a black product, while the reaction of the dilithio diamido salt with one equiv of [ZrCl 4 (THF) 2 ] in refluxing toluene affords the dinuclear zirconium derivative [Zr{1,2-C 6 H 4 (NCH 2 t Bu) 2 }Cl(THF)(μ-Cl)] 2 ( 2 ), obtained as an orange solid. Treatment of the dilithio diamido salt with TaCl 5 in a 2:1 molar ratio in toluene yields [Ta{1,2-C 6 H 4 (NCH 2 t Bu) 2 } 2 Cl] ( 3 ) as a red product. The reaction of 1,2-C 6 H 4 (NHCH 2 t Bu) 2 with [Zr(NMe 2 ) 4 ] in toluene at room temperature …
Bis(3,5-dimethylpyrazol-1-ato) zirconium complexes as precursors for ethylene polymerisation upon activation with MAO: Syntheses, characterisation and X-ray molecular structure of [Zr(η2-3,5-Me2Pz)2Cl2(η1-3,5-Me2PzH)2]·(3,5-Me2PzH) and [Zr(η2-3,5-Me2Pz)2(CH2Ph)2] (3,5-Me2Pz=3,5-dimethylpyrazol-1-ato)
Abstract The bis(3,5-dimethylpyrazol-1-ato) zirconium complex [Zr(η2-3,5-Me2Pz)2(NMe2)2(NHMe2)2] (2) is obtained by treatment of [Zr(NMe2)4] with 2 equiv. of 3,5-dimethylpyrazole 1. The reaction of the [ZrCl4(THF)2] adduct with 2 equiv. of the potassium salt of 1 affords the dichloro derivative [Zr(η2-3,5-Me2Pz)2Cl2]n (3), while reaction with 4.1 equiv. of 1 in the presence of 2.1 equiv. of NEt3 affords the dichloro pyrazole adduct [Zr(η2-3,5-Me2Pz)2Cl2(η1-3,5-Me2PzH)2] (4). Treatment of [Zr(CH2Ph)4] with 2 equiv. of 1 gives the dibenzyl complex [Zr(η2-3,5-Me2Pz)2(CH2Ph)2] (5) via alkane elimination. Compound 4 presents fluxional behaviour in CDCl3 solution, which was studied and quantified…