A 2-indenyl-amido-bridged titanium complex with Cs-symmetry

Weiß, Thomas; Becke, Sigurd; Sachse, H.; Rheinwald, Gerd; Lang, Heinrich

doi:10.1016/s1387-7003(01)00364-1

Cited by 5 publications

(2 citation statements)

References 16 publications

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“…Commercially available reagents were used without further purification. Methylindene,55 α‐pinenylpotassium,37 2‐(chlorodimethylsilyl)indene38 and 1‐(chlorodimethylsilyl)indene39 were synthesized essentially according to literature procedures. Chloro{[(1 S ,2 S ,5 S )‐6,6‐dimethylbicyclo[3.1.1]hept‐2‐yl]methyl}dimethylsilane was prepared by hydrosilylation of β‐pinene with chlorodimethylsilane in the presence of Karstedt’s catalyst 56,57.…”

Section: Methodsmentioning

confidence: 99%

“…[36] Finally, in a complementary approach, we investigated the possibility of using α-pinene as the chiral indenyl substituent. By deprotonation of α-pinene with nBuLi/tBuOK at 50°C using excess α-pinene [37] and the subsequent reaction of the obtained α-pinenyl potassium salt with 2-(chlorodimethylsilyl)indene [38] 21 or 1-(chlorodimethylsilyl)-indene [39] (1R)-23a/(1S)-23b, the corresponding 1-and 2-chirally substituted indenes 22 and (1R)-24a/(1S)-24b/25 were obtained in low (3 % and 21 %, respectively) yields (Scheme 8 and Scheme 9). The amount of the 3-silyl isomer 25 in the 24a/24b/25 mixture was estimated to 15 % by 1 H NMR spectroscopy.…”

Section: Ligand Precursor and Metallocene Synthesismentioning

confidence: 99%

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Chiral Indenes and Group‐4 Metallocene Dichlorides Containing α‐ and β‐Pinenyl‐Derived Ligand Substituents: Synthesis and Catalytic Applications in Polymerization and Carboalumination Reactions

et al. 2005

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The synthesis and characterization of chiral bis(indenyl)zirconium dichlorides containing β-pinenyl-derived ligand substituents is reported. Unbridged metallocene complexes having the {[(1S,2S,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-yl]methyl}dimethylsilyl substituent in both 1-and 2-positions of the indenyl moiety were prepared and isolated in moderate to low yields by reaction of the corresponding indenyllithium salts with ZrCl 4 followed by work-up and crystallization procedures. The corresponding tetrahydroindenyl complexes were obtained in excellent yields by catalytic hydrogenation of the indenyl six-membered rings. In a complementary approach, a synthetic route to α-pinenyl-substituted indenyl ligand analogues was briefly evaluated, which however, suffered from low yields. Selected β-pinenyl-substituted indenyl complexes were scanned as catalysts for the

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Section: Methodsmentioning

confidence: 99%

Section: Ligand Precursor and Metallocene Synthesismentioning

confidence: 99%

Chiral Indenes and Group‐4 Metallocene Dichlorides Containing α‐ and β‐Pinenyl‐Derived Ligand Substituents: Synthesis and Catalytic Applications in Polymerization and Carboalumination Reactions

et al. 2005

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Synthesis, characterization and soft transformation of some bis(cyclopentadienyl) Ti(IV) and Zr(IV) complexes of Schiff's base ligands to nano‐sized titania or zirconia materials

Sharma

Bohra

et al. 2007

Applied Organom Chemis

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Indenyl‐Titanchloride: Ethen‐Polymerisation und Struktur‐Reaktivitäts‐Untersuchungen

Weiß

Völkening

Rüffer

et al. 2007

Zeitschrift anorg allge chemie

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The halfsandwich complexes [(η 5 -C 9 H 7 )TiCl 3 ] (3a), [(η 5 -Me 3 Si-1-C 9 H 6 )TiCl 3 ] (3b), [(η 5 -Me-1-C 9 H 6 )TiCl 3 ] (3c), [(η 5 -Me 2 -4,7-C 9 H 5 )TiCl 3 ] (3d), [(η 5 -Me 3 Si-2-C 9 H 6 )TiCl 3 ] (3e), [(η 5 -Me 2 Ϫ1,3-C 9 H 5 )TiCl 3 ] (3f), [(η 5 -(CH 2 ) 3 Ϫ5,6-C 9 H 5 )TiCl 3 ] (4), and [(η 5 -(CH 2 ) 3 Ϫ1,7-C 9 H 5 )TiCl 3 ] (5) are accessible by reacting the in position 1 or 3 Me 3 Si-functionalized appropriate indenes with TiCl 4 . CG-TiCl 2 compounds (CG ϭ Constraint Geometry) can be synthesized by the subsequent reaction of Br-2-C 9 H 7 (6a), Br-2-Me 2 -1,3-C 9 H 5 (6b) and Br-2-(CH 2 ) 3 -5,6-C 9 H 5 (6c), respectively, with magnesium in presence of Me 2 SiCl 2 to give the respective Me 2 SiCl-functionalized indenes which further react with an excess of H 2 N t Bu to afford t BuHN-SiMe 2 -2-C 9 H 7 (8a), t BuHN-2-Me 2 -1,3-C 9 H 5 (8b) and t BuHNϪ2-(CH 2 ) 3 -5,6-C 9 H 5 (8c). The latter species produce on their consecutive reaction with n BuLi, [TiCl 3 ·3Thf] and PbCl 2 the titanium CG-complexes [(η 5 -SiMe 2 N t Bu-2-C 9 H 6 )TiCl 2 ] (9a), [(η 5 -Me 2 -1,3-SiMe 2 N t Bu-2-C 9 H 4 )TiCl 2 ] (9b), and [(η 5 -Me 2 SiN t Bu-2-(CH 2 ) 3 -5,6-C 9 H 4 )TiCl 2 ] (10). The same synthe- Chem. 2007, 633, 2242Ϫ2254 sis protocol allows the preparation of [(η 5 -Me 2 SiN t Bu-1-Me 3 Si-2-C 9 H 5 )TiCl 2 ] (12) a CG complex in which the Me 2 SiN t Bu unit is located in position 1. The polymerization of ethene by using 3Ϫ5 and 9Ϫ12 and MAO (MAO ϭ methylaluminoxane) as cocatalyst is described to show if a strong activity correlation between 3Ϫ5 and 9Ϫ12 exists. In order to optimize the catalytic activity of 3Ϫ5 the electronic (cyclic voltammetry, UV-Vis spectroscopy) and steric properties (Multiple Overlap Solid Angle) of these species were analyzed. Based on the obtained data, semi-empirical structure-activity models for 3Ϫ5 are proposed to obtain an optimized substituent pattern for the indenyl moiety. Substituents in position 1 or 4 of the appropriate indenyl π-perimeters show a strong bathochromic (ϩM) and electro-neutral to electro-negativ effect (0/-I).

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A 2-indenyl-amido-bridged titanium complex with Cs-symmetry

Cited by 5 publications

References 16 publications

Chiral Indenes and Group‐4 Metallocene Dichlorides Containing α‐ and β‐Pinenyl‐Derived Ligand Substituents: Synthesis and Catalytic Applications in Polymerization and Carboalumination Reactions

Chiral Indenes and Group‐4 Metallocene Dichlorides Containing α‐ and β‐Pinenyl‐Derived Ligand Substituents: Synthesis and Catalytic Applications in Polymerization and Carboalumination Reactions

Synthesis, characterization and soft transformation of some bis(cyclopentadienyl) Ti(IV) and Zr(IV) complexes of Schiff's base ligands to nano‐sized titania or zirconia materials

Indenyl‐Titanchloride: Ethen‐Polymerisation und Struktur‐Reaktivitäts‐Untersuchungen

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