Zirconium Complex of an [OSSO]-Type Diphenolate Ligand Bearing <i>trans</i>-1,2-Cyclooctanediylbis(thio) Core: Synthesis, Structure, and Isospecific 1-Hexene Polymerization

Ishii, Akihiko; Toda, Tomoyuki; Nakata, Norio; Matsuo, Tsukasa

doi:10.1021/ja903369q

Cited by 66 publications

(67 citation statements)

References 20 publications

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“…Recently, Ishii and co-workers have reported a zirconium complex of a tetradentate [OSSO]-type diphenolate ligand that bears a trans-1,2-cyclooctane diylbisA C H T U N G T R E N N U N G (thio)core and was effective in isospecific 1-hexene polymerization. [4] In material science or chemical research, the rational design of new o-carborane-derived materials has attracted much attention.…”

Section: Introductionmentioning

confidence: 99%

“…ZrCl 4 and HfCl 4 were treated with 1 a to give six-coordinated zirconium complex [Zr(OC 6 H 2 tBu 2 -4,6) 2 -…”

Section: Introductionmentioning

confidence: 99%

“…The O-Ti-O bond is bent toward the carborane by 19.48 from ideal linearity. Notably, treatment of ligand 1 a with TiA C H T U N G T R E N N U N G (OiPr) 4 that contained bulky isopropoxy groups under the same reaction conditions led to four-coordinate titanium complex 2 b. The molecular structure of 2 b was unambiguously determined by X-ray crystallography ( Figure 3); crystallographic data and processing parameters are given in Table 1.…”

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confidence: 99%

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Preparation, Structure, and Ethylene (Co)Polymerization Behavior of Group IV Metal Complexes with an [OSSO]‐Carborane Ligand

Wang

Jin

2011

Chemistry A European J

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The synthesis of Group IV metal complexes that contain a tetradentate dianionic [OSSO]-carborane ligand [(HOC(6)H(2)tBu(2)-4,6)(2)(CH(2))(2)S(2)C(2 (B(10)H(10))] (1a) is described. Reactions of TiCl(4) and Ti(OiPr)(4) with the [OSSO]-type ligand 1a afford six-coordinated titanium complex [Ti(OC(6)H(2)tBu(2)-4,6)(2)(CH(2))(2)S(2)C(2)(B(10)H(10))Cl(2)] (2a) and four-coordinated titanium complex [Ti(OC(6)H(2)tBu(2)-4,6)(2)(CH(2))(2)S(2)C(2)(B(10)H(10))(OiPr)(2)] (2b), respectively. ZrCl(4) and HfCl(4) were treated with 1a to give six-coordinated zirconium complex [Zr(OC(6)H(2)tBu(2)-4,6)(2)(CH(2))(2)S(2)C(2)(B(10)H(10))Cl(2) (thf)(2)] (2c) and six-coordinated hafnium complex [Hf(OC(6)H(2)tBu(2)-4,6)(2)(CH(2))(2)S(2)C(2)(B(10)H(10))Cl(2)] (2d). All the complexes were fully characterized by IR, NMR spectroscopy, and elemental analysis. In addition, X-ray structure analyses were performed on complexes 2a and 2b and reveal the expected different coordination geometry due to steric hindrance effects. Extended X-ray absorption fine structure (EXAFS) spectroscopy was performed on complexes 2c and 2d to describe the coordination chemistry of this ligand around Zr and Hf. Six-coordinated titanium complex 2a showed good activity toward ethylene polymerization as well as toward copolymerization of ethylene with 1-hexene in the presence of methylaluminoxane (MAO) as cocatalyst (up to 1060 kg[mol(Ti)](-1) h(-1) in the case of 10 atm of ethylene pressure).

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Section: Introductionmentioning

confidence: 99%

“…ZrCl 4 and HfCl 4 were treated with 1 a to give six-coordinated zirconium complex [Zr(OC 6 H 2 tBu 2 -4,6) 2 -…”

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Preparation, Structure, and Ethylene (Co)Polymerization Behavior of Group IV Metal Complexes with an [OSSO]‐Carborane Ligand

Wang

Jin

2011

Chemistry A European J

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“…For example, catalysts based on phenoxy-imine complexes may be not only more active than the metallocene catalysts, but they make it possible to produce a variety of polyolefinic materials, inclusive of ultra-high-molecular-weight PEs, welldefined multimodal PEs, selective vinyl-and Al-terminated PEs, isotactic and syndiotactic PPs, as well as stereo-and regioirregular high-molecular weight poly(1-olefin)s [1]. Group 4 transition metal complexes which incorporate tetradentate [OSSO]-type bis(phenolate) ligands have also been quite extensively studied in homo-and copolymerization of olefins as well as in polymerization of styrene and its derivatives, and in olefin-styrene copolymerization [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The titanium complex of the tetradentate [OSSO]-type diphenolate ligand with the 1,4-dithiabutanediyl-bridge yielded isotactic PS at very high activity.…”

Section: Introductionmentioning

confidence: 99%

“…The zirconium complex produced exclusively oligomers with even numbers of carbon atoms while its titanium analogue gave branched polymers [9,12]. Another zirconium complex as well as the hafnium one, having a ligand bearing trans-1,2-cyclooctanediylbis(thio) core, were highly active in 1-hexene polymerization providing highly isotactic poly(1-hexene) [15,16]. It was also shown that the regioselectivity during 1-hexene oligomerization switched when the titanium metal center was replaced with its heavier homolog (Zr, Hf) [10].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and olefin homo- and copolymerization behavior of new vanadium complexes bearing [OSSO]-type ligands

Białek

Fryga

Spaleniak

et al. 2017

Reac Kinet Mech Cat

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Novel vanadium complexes bearing [OSSO]-type ligands having two phenolato units linked through the -CH 2 S(CH 2 ) 4 SCH 2 -(1V) or -CH 2 S(CH 2 ) 2-SCH 2 -(2V) bridge are synthesized with good yields by reacting a deprotonated ligand with VCl 4 . They are then used in ethylene (co)polymerization after activation with EtAlCl 2 and Et 2 AlCl. In the presence of EtAlCl 2 , both complexes promote ethylene polymerization with very high activities, over 4 9 10 7 g/(mol h), leading to PEs with high molecular weight and narrow molecular weight distribution. The prepared complexes exhibit lower activity for ethylene/1-octene copolymerization. It is also revealed that the catalyst based on the -CH 2 S(CH 2 ) 4 SCH 2 -bridged complex shows both higher activity and higher comonomer incorporation ability than the catalyst based on the -CH 2 S(CH 2 ) 2 SCH 2 -bridged complex. Upon activation with Al(iBu) 3 /Ph 3 CB(C 6 F 5 ) 4 , complex 2V produces stereo-and regioirregular poly(1-octene), while 1V gives the isotactically enriched product.

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Stereoregular Polymers

Takeuchi

2013

Encyclopedia of Polymer Science and Technology

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Control of structure of polymers is an important issue in polymer synthesis because it affects properties such as solubility, crystallinity, and thermal properties. The polymers having stereogenic centers on a main chain can be synthesized by vinyl polymerization of olefinic monomers or ring-opening polymerization of cyclic monomers. Control of trans-cis selectivity is also important for the polymers containing C C double bonds in the main chain. The progress of homogeneous metal complex catalysts for coordination and ring-opening polymerization enables tailor-made control of the stereoregularity of the polymers. In this article, general aspects of stereoregular polymers, especially the polymer of monosubstituted vinyl monomers, are described. Recent progress in stereospecific polymerization of propylene, α-olefins, and styrenes is also summarized. Propylene Polymerization.Isospecific Polymerization of Propylene by Ziegler-Natta Catalysts. In 1954, Natta found that TiCl 3 /Et 2 AlCl catalyst is effective for the synthesis of isotactic polypropylene (4,5). Ti(III) is the active species of the polymerization, whereas other Ti species are also included in the catalyst. Moreover, the stereospecific Ti(III) site as well as nonstereospecific Ti(III) site exists in the catalyst.

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Zirconium Complex of an [OSSO]-Type Diphenolate Ligand Bearing trans-1,2-Cyclooctanediylbis(thio) Core: Synthesis, Structure, and Isospecific 1-Hexene Polymerization

Cited by 66 publications

References 20 publications

Preparation, Structure, and Ethylene (Co)Polymerization Behavior of Group IV Metal Complexes with an [OSSO]‐Carborane Ligand

Preparation, Structure, and Ethylene (Co)Polymerization Behavior of Group IV Metal Complexes with an [OSSO]‐Carborane Ligand

Synthesis and olefin homo- and copolymerization behavior of new vanadium complexes bearing [OSSO]-type ligands

Stereoregular Polymers

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