The catalytic behavior of heterocenes activated by TIBA and MMAO under a low Al/Zr ratios in 1-octene polymerization

Nifant’ev, Ilya E.; Vinogradov, Alexander A.; Vinogradov, A.; Churakov, Andrei V.; Bagrov, Vladimir V.; Kashulin, I. A.; Roznyatovsky, Vitaly A.; Grishin, Yuri K.; Ivchenko, Pavel V.

doi:10.1016/j.apcata.2018.12.006

Cited by 26 publications

(30 citation statements)

References 71 publications

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“…[10][11][12][13][14][15] Recently, we demonstrated the high efficiency of cyclopenta[b] thiophene Zr complexes in oligomerization of C 6 -C 10 a-olens, 16 and the promising catalytic properties of Zr ansa-complexes based on cyclopenta[1,2-b:4,3-b 0 ]dithiophene, indeno [1,2-b] indole and indeno [2,1-b]indole (Scheme 2, top) in polymerization of 1-octene. 17 In our experiments, heterocenes outperformed traditional cyclopentadienyl, indenyl and uorenyl sandwich Scheme 1 Donor heterocyclefused cyclopentadienes.…”

Section: Introductionmentioning

confidence: 69%

“…were synthesized according to previously reported procedures (see also 17 and Section S1 in the ESI †). 11-Phenyl-6H-indeno[1,2-b]indolizine 4 is a new compound that was prepared by Scheme 3 (see Section S1 in the ESI † for NMR spectra).…”

Section: Resultsmentioning

confidence: 99%

“…The molecular structure of these compounds is poorly studied; to date, only a few dichlorozirconium ansa-complexes have been characterized by X-ray diffraction analysis. 10,17,[19][20][21][22][23][24] Obviously, these data do not reect the entire spectrum of possible metal-ligand interactions in catalytic species due to the predominantly covalent nature of bonding in neutral LZrCl 2 complexes.…”

Section: Introductionmentioning

confidence: 88%

“…The analysis of the structures of heterocycle-fused cyclopentadienides allows us to conclude that the presence of annelated donor heterocycle instead of condensed benzene ring (Scheme 5) does not lead to signicant changes in the geometry of C5 and C6 rings compared to uorenide. Apparently, the possible causes of the difference observed in NMR spectra, and in the chemical behavior of zirconium complexes based on uorene and 5-7, 17 can be attributed to the difference in the electronic structure of these ligands.…”

Section: Crystallographic Study Of Potassium Saltsmentioning

confidence: 99%

“…This behavior indicates that heterocene ligands much more effectively stabilize the Zr cationic reaction center relative to traditional cyclopentadienides due to their electron-donor nature, 18 which entails increasing in catalytic activity and feasibility of using heterocenes at elevated temperatures. The structural diversity of heterocycle-fused cyclopentadienes permits a more variety in stereocontrol of a-olen insertion: rac-forms of ansa-zirconocenes based on heteroanalogs of indene allows to obtain isotactic polypropylene 19 or polypropylene elastomers; 20,21 Zr complexes based on heteroanalogs of uorene were successfully used in the synthesis of polypropylene elastomers, 11,14,15 isotactic poly(1-butene), 12 high MW atactic polyolens 17 and other prospective materials.…”

Section: Introductionmentioning

confidence: 99%

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The structural diversity of heterocycle-fused potassium cyclopentadienides

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Section: Introductionmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 88%

Section: Crystallographic Study Of Potassium Saltsmentioning

confidence: 99%

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confidence: 99%

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The structural diversity of heterocycle-fused potassium cyclopentadienides

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Synthesis of Heteroarene‐Fused Cyclopentadienes and Related Compounds Suitable for Metallocene Preparation

Nifant’ev

Ivchenko

2020

Adv Synth Catal

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Metallocene catalysis is widely used in transformations of unsaturated organic compounds, including the bulk industrial synthesis of polyolefins. Over the last few decades, the electronic and structural properties of their η5‐coordinated ligands have been modified by introducing electron‐donating, electron‐withdrawing, and sterically hindered substituents to obtain desirable catalytic properties for the metallocenes. An efficient way to design η5‐coordinated ligands is to exploit the annelation of heterocyclic fragments with a cyclopentadiene ring. In the present review, we summarize, systematize, and analyze synthetic approaches to heterocycle‐fused cyclopentadienes suitable for metallocene catalyst preparation.

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Unraveling the structure–property relationship of novel thiophene and furan‐fused cyclopentadienyl chromophores for nonlinear optical applications

Sun

2024

J Comput Chem

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Development of organic nonlinear optical materials has become progressively more important due to their emerging applications in new‐generation photonic devices. A novel series of chromophores based on innovative thiophene and furan‐fused cyclopentadienyl bridge with various powerful donor and acceptor moieties were designed and theoretically investigated for applications in nonlinear optics. To unravel the structure–property relationship between this new push‐pull conjugated systems and their nonlinear optical property, multiple methods, including density of states analysis, coupled perturbed Kohn–Sham (CPKS) method, sum‐over‐states (SOS) model, the two‐level model (TSM), hyperpolarizability density analysis, and the (hyper)polarizability contribution decomposition, were performed to comprehensively investigated the nonlinear optical and electronic properties of this new π‐system. Due to excellent charge transfer ability of new bridge and distinctive structure of donor and acceptor, the designed chromophores exhibit deep HOMO levels, low excitation energy, high dipole moment difference and large hyperpolarizability, indicating the appealing air‐stable property and remarkable electrooptic performance of them. Importantly, THQ‐CS‐A3 and PA‐CS‐A3 shows outstanding NLO response properties with βtot value of 6953.9 × 10−30 and 5066.0 × 10−30 esu in AN, respectively. The influence of the push‐pull strength, the heterocycle and the π‐conjugation of new bridge on the nonlinear optical properties of this novel powerful systems are clarified. This new series of chromophores exhibit remarkable electro‐optical Pockels and optical rectification effect. More interestingly, PA‐CS‐A3 and THQ‐CS‐A2 also show appealing SHG effect. This study will help people understand the nature of nonlinear optical properties of innovative heteroarene‐fused based cyclopentadienyl chromophores and offer guidance for the rational design of chromophores with outstanding electrooptic (EO) performance in the future.

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The catalytic behavior of heterocenes activated by TIBA and MMAO under a low Al/Zr ratios in 1-octene polymerization

Cited by 26 publications

References 71 publications

The structural diversity of heterocycle-fused potassium cyclopentadienides

The structural diversity of heterocycle-fused potassium cyclopentadienides

Synthesis of Heteroarene‐Fused Cyclopentadienes and Related Compounds Suitable for Metallocene Preparation

Unraveling the structure–property relationship of novel thiophene and furan‐fused cyclopentadienyl chromophores for nonlinear optical applications

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