Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F12%3A10127542" target="_blank" >RIV/00216208:11310/12:10127542 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/12:00383850

Výsledek na webu

<a href="http://dx.doi.org/10.1021/om300461k" target="_blank" >http://dx.doi.org/10.1021/om300461k</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/om300461k" target="_blank" >10.1021/om300461k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne

Popis výsledku v původním jazyce

Ethene complexes of titanocenes [Ti(II)(eta(2)-C2H4)(Cp')(2)] for Cp' = eta(5)-C5Me5 (1), eta(5)-C(5)Me(4)t-Bu (2), eta 5-C5Me4SiMe3 (3), and eta(5)-C5HMe4 (4) were prepared by reduction of corresponding titanocene dichlorides with magnesium in THF in the presence of ethene. Thermolysis of 1-3 in toluene solution at a maximum of 100 degrees C resulted in elimination of ethane, affording cleanly doubly tucked-in titanocene compounds 5-7, respectively. Experiments with 2 and 3 in NMR tubes proved that symmetrical isomers 6a and 7a were formed first, and these thermally isomerized to thermodynamically more stable asymmetrical isomers 6b and 7b. The energy difference between 7a and 7b calculated by DFT methods was 15.3 kJ/mol. Thermolysis of 4 in m-xylenerequired a temperature of 135 degrees C, affording a mixture of 8b > 8a and "dimeric dehydro-titanocene" 9 as a concurrent product of hydrogen abstraction. In contrast to thermolysis in solvents, heating of 1 and 2 in high vacuum to 135 d

Název v anglickém jazyce

Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne

Popis výsledku anglicky

Ethene complexes of titanocenes [Ti(II)(eta(2)-C2H4)(Cp')(2)] for Cp' = eta(5)-C5Me5 (1), eta(5)-C(5)Me(4)t-Bu (2), eta 5-C5Me4SiMe3 (3), and eta(5)-C5HMe4 (4) were prepared by reduction of corresponding titanocene dichlorides with magnesium in THF in the presence of ethene. Thermolysis of 1-3 in toluene solution at a maximum of 100 degrees C resulted in elimination of ethane, affording cleanly doubly tucked-in titanocene compounds 5-7, respectively. Experiments with 2 and 3 in NMR tubes proved that symmetrical isomers 6a and 7a were formed first, and these thermally isomerized to thermodynamically more stable asymmetrical isomers 6b and 7b. The energy difference between 7a and 7b calculated by DFT methods was 15.3 kJ/mol. Thermolysis of 4 in m-xylenerequired a temperature of 135 degrees C, affording a mixture of 8b > 8a and "dimeric dehydro-titanocene" 9 as a concurrent product of hydrogen abstraction. In contrast to thermolysis in solvents, heating of 1 and 2 in high vacuum to 135 d

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2012

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

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Svazek periodika

31

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

16

Strana od-do

5478-5493

Kód UT WoS článku

000307422200029

EID výsledku v databázi Scopus

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