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Chromocene-Cyclopentadienyltitanium Trichloride Ion Pairs and Their Rearrangement to Titanocene Chloride-Cyclopentadienylchromium Dichlorides Ethylene Polymerization Tests
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SYSNO ASEP 0492078 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Chromocene-Cyclopentadienyltitanium Trichloride Ion Pairs and Their Rearrangement to Titanocene Chloride-Cyclopentadienylchromium Dichlorides Ethylene Polymerization Tests Author(s) Varga, Vojtěch (UFCH-W) RID
Pinkas, Jiří (UFCH-W) RID, ORCID
Císařová, I. (CZ)
Kubišta, Jiří (UFCH-W) RID, ORCID
Horáček, Michal (UFCH-W) RID, ORCID
Mach, Karel (UFCH-W) ORCID, RID
Gyepes, Robert (UFCH-W) RID, ORCIDSource Title European Journal of Inorganic Chemistry. - : Wiley - ISSN 1434-1948
Roč. 2018, č. 23 (2018), s. 2637-2647Number of pages 11 s. Language eng - English Country DE - Germany Keywords transition-metal-complexes ; arene titanium catalysts ; olefin polymerization ; molecular-structures ; acetylene complexes ; chromium catalysts ; trimerization Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GA17-13778S GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000435936400004 EID SCOPUS 85048853813 DOI 10.1002/ejic.201800202 Annotation Reactions of chromocene [CrCp2] (Cp = (5)-C5H5) with cyclopentadienyltitanium trichlorides [Ti((5)-C5H5-nMen)Cl-3] (n = 0-5) and [Ti(C5Me4Et)TiCl3] in toluene resulted in precipitation of ion pairs of [CrCp2](+)[Ti((5)-C5H5-nMen)Cl-3](-) (1-6) and [CrCp2](+)[Ti((5)-C5Me4Et)Cl-3](-) (7). Heating their toluene solutions to 100 degrees C yielded the titanocene chloride cyclopentadienylchromium dichloride complexes with the metals linked by bridging chloride ligands. For n = 0-3, the purple-violet complexes [CpCpTi(mu-Cl)(2)Cr(Cp)Cl] (Cp cyclopentadienyl ligand of the titanium component) (8-11) were stable at 100 degrees C, and the single-crystal structure of [Cp2Ti(mu-Cl)(2)Cr(Cp)Cl] (8) was determined. The bridging complexes of the same type for n = 4, 5 and the C5Me4Et ligand (12-14) were contaminated with titanocene dichlorides containing mixed auxiliary ligands [TiCp(C5HMe4)Cl-2] (15), [TiCp(C5Me5)Cl-2] (16), and [TiCp(C5Me4Et)Cl-2] (17), respectively. In addition, they contained the hitherto unknown (CpCrCl)(n) (18). Heating of 12-14 to 100 degrees C resulted in their decomposition to 15-17, accompanied with 18 in all cases. The molecular and electronic properties of 1, 4, 5, 8 and both isomers of 13 were investigated by DFT. Complexes 8, 9, and 11 activated with MMAO polymerized ethylene in toluene to very high molecular weights polyethylene (M-n 500 kgmol(-1)). Upon activation with B(C6F5)(3)/Et3SiH in dichloromethane they produced M-n = 9-23 kgmol(-1). The titanium species was the catalytically dominant one in both cases. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2019
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