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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F08%3A00316214%21RIV09-AV0-61388955
rdf:type
n17:Vysledek skos:Concept
dcterms:description
Permethylovaný titanocen s jednou methylenovou vazbou 1 reaguje s nadbytkem interních alkinů za tvorby 1:1 produktů 3a-3c a 3f-3i vznikajících insercí trojné vazby do vazby titanu k methylenové skupině. Pouze v případě nejjednodušší molekuly 2-butinu dochází k inserci dvou molekul za vzniku známé sloučeniny 2, na druhé straně produkt inserce jedné molekuly 3j vzniká při stechiometrické reakci v poměru 1:1. 1,4-disubstituované konjugované diiny s CMe3 nebo SiMe3 substituenty reagují stejnou cestou, ale pouze jednou trojnou vazbou za vzniku sloučenin 3d a 3e. Dialkiny s dimethylsilylenovým můstkem Me2Si(C=CR)2 (R = SiMe3 nebo CMe3) poskytují reakcí obou trojných vazeb sloučeniny 3k a 3l. Po inserci první trojné vazby druhá podstupuje přesmyk, který vyústí v posunu substituentu a vzniku silacyklobutenového kruhu spojeného s atomem titanu. Alkiny nesoucí objemné substituenty CMe3 nebo SiMe3 byly nereaktivní. Single tucked-in permethyltitanocene 1 reacts with excess of internal alkynes to give 1:1 adducts 3a-3c and 3f-3i arising from insertion of their triple bond into the titanium-methylene bond. Only the simplest 2-butyne inserted two molecules to give the known compound 2, however, at a 1:1 stoichiometric ratio the 1:1 adduct 3j was also smoothly formed. 1,4-Disubstituted conjugated diynes with CMe3 or SiMe3 substituents reacted in the same way by only one triple bond to give 3d and 3e, respectively. The dimethylsilylene-bridged dialkynes Me2Si(C=CR)2 (R = SiMe3 or CMe3) afforded compounds 3k and 3l with both triple bonds reacting. After insertion of the first triple bond the second one underwent a rearrangement which resulted in substituent shift and formation of a silacyclobutene ring linked to the titanium atom. The alkynes bearing both bulky substituents CMe3 or SiMe3 were unreactive. Single tucked-in permethyltitanocene 1 reacts with excess of internal alkynes to give 1:1 adducts 3a-3c and 3f-3i arising from insertion of their triple bond into the titanium-methylene bond. Only the simplest 2-butyne inserted two molecules to give the known compound 2, however, at a 1:1 stoichiometric ratio the 1:1 adduct 3j was also smoothly formed. 1,4-Disubstituted conjugated diynes with CMe3 or SiMe3 substituents reacted in the same way by only one triple bond to give 3d and 3e, respectively. The dimethylsilylene-bridged dialkynes Me2Si(C=CR)2 (R = SiMe3 or CMe3) afforded compounds 3k and 3l with both triple bonds reacting. After insertion of the first triple bond the second one underwent a rearrangement which resulted in substituent shift and formation of a silacyclobutene ring linked to the titanium atom. The alkynes bearing both bulky substituents CMe3 or SiMe3 were unreactive.
dcterms:title
Insertion of internal alkynes and ethene into permethylated single tucked-in titanocene Inserce interních alkinů a ethylenu do permethylovaného titanocenu s jednou methylenovou vazbou Insertion of internal alkynes and ethene into permethylated single tucked-in titanocene
skos:prefLabel
Inserce interních alkinů a ethylenu do permethylovaného titanocenu s jednou methylenovou vazbou Insertion of internal alkynes and ethene into permethylated single tucked-in titanocene Insertion of internal alkynes and ethene into permethylated single tucked-in titanocene
skos:notation
RIV/61388955:_____/08:00316214!RIV09-AV0-61388955
n3:aktivita
n16:V n16:Z n16:P
n3:aktivity
P(IAA400400708), P(LC06070), V, Z(AV0Z40400503)
n3:cisloPeriodika
21
n3:dodaniDat
n15:2009
n3:domaciTvurceVysledku
n8:9689907 n8:7016662 n8:7763743 n8:7277962 n8:6327230
n3:druhVysledku
n18:J
n3:duvernostUdaju
n13:S
n3:entitaPredkladatele
n14:predkladatel
n3:idSjednocenehoVysledku
372586
n3:idVysledku
RIV/61388955:_____/08:00316214
n3:jazykVysledku
n5:eng
n3:klicovaSlova
alkynes; titanocene; ethene
n3:klicoveSlovo
n7:alkynes n7:ethene n7:titanocene
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[07110C2224AE]
n3:nazevZdroje
Organometallics
n3:obor
n11:CF
n3:pocetDomacichTvurcuVysledku
5
n3:pocetTvurcuVysledku
9
n3:projekt
n10:IAA400400708 n10:LC06070
n3:rokUplatneniVysledku
n15:2008
n3:svazekPeriodika
27
n3:tvurceVysledku
Kubišta, Jiří Čejka, Jiří Hey-Hawkins, E. Mach, Karel Pinkas, Jiří Horáček, Michal Císařová, I. Gómez-Ruiz, S. Gyepes, R.
n3:wos
000260383900019
n3:zamer
n4:AV0Z40400503
s:issn
0276-7333
s:numberOfPages
16