Chromocene-Cyclopentadienyltitanium Trichloride Ion Pairs and Their Rearrangement to Titanocene Chloride-Cyclopentadienylchromium Dichlorides Ethylene Polymerization Tests

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00492078" target="_blank" >RIV/61388955:_____/18:00492078 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/18:10376992

Výsledek na webu

<a href="http://dx.doi.org/10.1002/ejic.201800202" target="_blank" >http://dx.doi.org/10.1002/ejic.201800202</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.201800202" target="_blank" >10.1002/ejic.201800202</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chromocene-Cyclopentadienyltitanium Trichloride Ion Pairs and Their Rearrangement to Titanocene Chloride-Cyclopentadienylchromium Dichlorides Ethylene Polymerization Tests

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Chromocene-Cyclopentadienyltitanium Trichloride Ion Pairs and Their Rearrangement to Titanocene Chloride-Cyclopentadienylchromium Dichlorides Ethylene Polymerization Tests

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA17-13778S" target="_blank" >GA17-13778S: Hliník neobsahující katalytický systém využívající hydrosilan-B(C6F5)3 adukty jako aktivátory přechodných kovů při polymeraci ethylenu</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

—

Svazek periodika

2018

Číslo periodika v rámci svazku

23

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

2637-2647

Kód UT WoS článku

000435936400004

EID výsledku v databázi Scopus

2-s2.0-85048853813