Synthesis, crystal structure and ethylene polymerization activity of zirconium complexes bearing mono-Cp and tridentate Schiff base [ONO] ligands

Chen, Qihui; Huang, Jiling; Yu, Jing

doi:10.1016/j.inoche.2005.02.005

Cited by 29 publications

(9 citation statements)

References 28 publications

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“…The 1 H and 13 C NMR spectra for 1 − 7 were analogous to those reported previously. − For instance, a resonance ascribed to the imino protons in 1 was observed at 8.54 ppm, which is slightly downfield from that in the corresponding free imino phenol (8.28 ppm); a resonance ascribed to the imino carbon in 1 was observed at 156.9 ppm, whereas the resonance in the free ligand was observed at 159.2 ppm.…”

Section: Resultssupporting

confidence: 79%

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Synthesis of Half-Titanocenes Containing Phenoxy-imine Ligands and Their Use as Catalysts for Olefin Polymerization

et al. 2007

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Various half-titanocenes containing phenoxy-imine ligands of the type Cp‘TiCl2[O-2-R1-6-(R2NCH)C6H3] [Cp‘ = Cp* (C5Me5) and R1, R2 = Me, 2,6- i Pr2C6H3 (1); t Bu, 2,6- i Pr2C6H3 (2); Me, t Bu (3); t Bu, t Bu (4); Cp‘ = 1,2,4-Me3C5H2 and R1, R2 = Me, 2,6- i Pr2C6H3 (5); Cp‘ = Cp and R1, R2 = Me, 2,6- i Pr2C6H3 (6); Me, t Bu (7)] were prepared by reaction of Cp‘TiCl3 with LiO-2-R1-6-(R2NCH)C6H3 that were prepared in situ by treating the corresponding phenol with n-BuLi. Cp*TiMe2[O-2-Me-6-{(2,6- i Pr2C6H3)NCH}C6H3] (8) was prepared from Cp*TiMe3 by treating with 2-Me-6-{(2,6- i Pr2C6H3)NCH}C6H3OH in n-hexane, and the reaction with [PhN(H)Me2][B(C6F5)4] was also explored. Structures for 1−3 and 5−8 were determined by X-ray crystallography, and the imino nitrogen in the phenoxy-imine ligand was not coordinated to Ti in all cases; the bond angles for Ti−O−C(Ph) were affected by substituents in both cyclopentadienyl and phenoxy-imine ligands. The catalytic activities for ethylene polymerization and syndiospecific styrene polymerization using 1−7−MAO catalyst systems were highly affected by the substituents in both cyclopentadienyl and phenoxy-imine ligands; the Cp* analogues (3, 4) exhibited notable activities for ethylene polymerization, whereas the Cp analogues (6, 7) showed significant activities for syndiospecific styrene polymerization. The Cp analogue 6 was also an effective catalyst precursor for copolymerization of ethylene with norbornene.

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Section: Resultssupporting

confidence: 79%

“…Recently, we (group of Qian and Huang) and Bochmann reported synthesis of half-titanocenes containing phenoxy-imine ligands (e.g., CpTiCl 2 [O-2- t Bu-6-(RNCH)C 6 H 3 ], R = 2,4,6-Me 3 C 6 H 2 , C 6 F 5 , C 6 H 11 , etc.) and their use as the catalyst precursors for olefin polymerization.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Half-Titanocenes Containing Phenoxy-imine Ligands and Their Use as Catalysts for Olefin Polymerization

et al. 2007

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“…These salicylaldiminato ligands are obtained by easy synthetic routes, and hence their steric and electronic properties can be readily tuned, via substitution of the aromatic ring or modification of the imino nitrogen substitutent. However, despite extensive investigation of group IV metal complexes of salicylaldiminato ligands and their utilities in olefin polymerization chemistry, few monocyclopentadienyl salicylaldiminato group IV metal derivatives of the type Cp‘M[ON] n X 3- n (M = Ti, Zr; Cp‘ = substituted or unsubstituted cyclopentadienyl ring; L = bidentate monoanionic salicylaldiminato ligand; X = anionic donor ligand) have been reported …”

Section: Introductionmentioning

confidence: 99%

“…The most active systems were demonstrated to be effective for the copolymerization of 1-hexene and ethylene. In the absence of ethylene, 1-hexene is oligomerized 5b 5a,c Recently, half-sandwich monochloro and monoalkyl group IV metal complexes CpZr[ONNO]Cl ([ONNO] = [C 6 H 4 -1,2-{NCH(3,5- t Bu 2 C 6 H 2 -2-O)} 2 ]) containing tetradentate dianionic salicylaldiminato ligands have been developed.…”

Section: Introductionmentioning

confidence: 99%

“…In the absence of ethylene, 1-hexene is oligomerized 5b 5a,c Recently, half-sandwich monochloro and monoalkyl group IV metal complexes CpZr[ONNO]Cl ([ONNO] = [C 6 H 4 -1,2-{NCH(3,5- t Bu 2 C 6 H 2 -2-O)} 2 ]) containing tetradentate dianionic salicylaldiminato ligands have been developed. The zirconium complexes are catalyst precursors for the polymerization of ethylene when activated with MAO under mild conditions 5c.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Ethylene Polymerization of Group IV Metal Complexes with Mono-Cp and Tridentate Aryloxide or Arylsulfide Ligands

2007

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Half-sandwich titanium and zirconium complexes with tridentate dianionic aryloxide or arylsulfide ligands [R-2-{(2-XC6H4)NCH}C6H2O]2- ([XNOR]2-, R = H, X = O (L1); R = 4-Me-6-Bu t (R‘), X = O (L2); R = H, X = S (L3); R = 4-Me-6-Bu t (R‘), X = S (L4)) have been prepared. Reactions of CpMCl3 (M = Ti, Zr) with sodium salts of the aryloxide or arylsulfide ligands (L1−L4) afford CpTi[XNOR]Cl [R = H, X = O (1); R = 4-Me-6-Bu t (R‘), X = O (2); R = H, X = S (3); R = 4-Me-6-Bu t (R‘), X = S (4)] and CpZr[ONOR]Cl [R = H (5)], respectively. Complexes 1−5 were characterized by IR and 1H NMR spectra and elemental analyses, and their molecular structures have been determined by X-ray diffraction methods. The coordination properties of these complexes have been investigated in the solid state and compared to related systems. When activated by excess methylaluminoxane (MAO), these complexes can be used as catalysts for ethylene polymerization and exhibited moderate activities. The activities of arylsulfide complexes 3 and 4 are higher than those of their analogues, aryloxide complexes 1 and 2, and zirconium complex 5 is much more active than titanium complexes 1−4.

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Synthesis of novel zirconium complexes bearing mono‐Cp and tridentate Schiff base [ONO] ligands and their catalytic activities for olefin polymerization

Chen

Huang

2006

Applied Organom Chemis

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Synthesis, crystal structure and ethylene polymerization activity of zirconium complexes bearing mono-Cp and tridentate Schiff base [ONO] ligands

Cited by 29 publications

References 28 publications

Synthesis of Half-Titanocenes Containing Phenoxy-imine Ligands and Their Use as Catalysts for Olefin Polymerization

Synthesis of Half-Titanocenes Containing Phenoxy-imine Ligands and Their Use as Catalysts for Olefin Polymerization

Synthesis, Characterization, and Ethylene Polymerization of Group IV Metal Complexes with Mono-Cp and Tridentate Aryloxide or Arylsulfide Ligands

Synthesis of novel zirconium complexes bearing mono‐Cp and tridentate Schiff base [ONO] ligands and their catalytic activities for olefin polymerization

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