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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F12%3A00383850%21RIV13-GA0-61388955
rdf:type
n8:Vysledek skos:Concept
dcterms:description
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-xylene required a temperature of 135 degrees C, affording a mixture of 8b > 8a and %22dimeric dehydro-titanocene%22 9 as a concurrent product of hydrogen abstraction. In contrast to thermolysis in solvents, heating of 1 and 2 in high vacuum to 135 degrees C resulted in sublimation of known titanocenes [Ti(C5Me5)(2)] (10) and [Ti(eta(5)-C(5)Me(4)t-Bu)(2)] (13) (Chink et al. J. Am. Chem. Soc. 2004, 126, 14688-14689), respectively. The former isomerized in hexane solution to the tucked-in hydride [TiH{C5Me4(CH2)}(C5Me5)] (10A) as described by Bercaw (J. Am. Chem. Soc. 2004, 126, 14688-14689). A mixture of 10/10A decayed within days to give major paramagnetic products [TiH(C5Me5)(2)] (11) and singly tucked-in titanocene [Ti{C5Me4(CH2)}(C5Me5)] (12) and minor diamagnetic 5 and its so far unknown, less stable isomer [Ti{C5Me4(CH2)}(2)] (10B), identified by NMR spectra and corroborated by DFT calculations. Solid 3 eliminated ethene at only 80 degrees C, leaving titanocene 14, whereas compound 4 sublimed at 135 degrees C mostly without decomposition. 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-xylene required a temperature of 135 degrees C, affording a mixture of 8b > 8a and %22dimeric dehydro-titanocene%22 9 as a concurrent product of hydrogen abstraction. In contrast to thermolysis in solvents, heating of 1 and 2 in high vacuum to 135 degrees C resulted in sublimation of known titanocenes [Ti(C5Me5)(2)] (10) and [Ti(eta(5)-C(5)Me(4)t-Bu)(2)] (13) (Chink et al. J. Am. Chem. Soc. 2004, 126, 14688-14689), respectively. The former isomerized in hexane solution to the tucked-in hydride [TiH{C5Me4(CH2)}(C5Me5)] (10A) as described by Bercaw (J. Am. Chem. Soc. 2004, 126, 14688-14689). A mixture of 10/10A decayed within days to give major paramagnetic products [TiH(C5Me5)(2)] (11) and singly tucked-in titanocene [Ti{C5Me4(CH2)}(C5Me5)] (12) and minor diamagnetic 5 and its so far unknown, less stable isomer [Ti{C5Me4(CH2)}(2)] (10B), identified by NMR spectra and corroborated by DFT calculations. Solid 3 eliminated ethene at only 80 degrees C, leaving titanocene 14, whereas compound 4 sublimed at 135 degrees C mostly without decomposition.
dcterms:title
Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne
skos:prefLabel
Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne
skos:notation
RIV/61388955:_____/12:00383850!RIV13-GA0-61388955
n8:predkladatel
n9:ico%3A61388955
n3:aktivita
n13:Z n13:P n13:I
n3:aktivity
I, P(GAP207/12/2368), P(GP203/09/P276), Z(MSM0021620857)
n3:cisloPeriodika
15
n3:dodaniDat
n19:2013
n3:domaciTvurceVysledku
n11:6327230 n11:7277962 n11:5347440 n11:9689907 n11:7763743
n3:druhVysledku
n15:J
n3:duvernostUdaju
n12:S
n3:entitaPredkladatele
n4:predkladatel
n3:idSjednocenehoVysledku
134838
n3:idVysledku
RIV/61388955:_____/12:00383850
n3:jazykVysledku
n20:eng
n3:klicovaSlova
titanocenes; ethene complexes; thermolysis
n3:klicoveSlovo
n16:thermolysis n16:ethene%20complexes n16:titanocenes
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[B0EC80F9D953]
n3:nazevZdroje
Organometallics
n3:obor
n5:CF
n3:pocetDomacichTvurcuVysledku
5
n3:pocetTvurcuVysledku
6
n3:projekt
n6:GP203%2F09%2FP276 n6:GAP207%2F12%2F2368
n3:rokUplatneniVysledku
n19:2012
n3:svazekPeriodika
31
n3:tvurceVysledku
Gyepes, Robert Horáček, Michal Císařová, I. Mach, Karel Pinkas, Jiří Kubišta, Jiří
n3:wos
000307422200029
n3:zamer
n17:MSM0021620857
s:issn
0276-7333
s:numberOfPages
16
n18:doi
10.1021/om300461k