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Statements

Subject Item
n2:RIV%2F00216208%3A11310%2F14%3A10272019%21RIV15-MSM-11310___
rdf:type
n20:Vysledek skos:Concept
rdfs:seeAlso
http://dx.doi.org/10.1021/om500296h
dcterms:description
New titanocene dihydrosulfide compounds [(C5Me4CH2Ph)(2)Ti(SH)(2)] (6) and [(C(5)Me(4)t-Bu)(2)Ti(SH)(2)] (7) were obtained by addition of hydrogen sulfide to the corresponding doubly tucked-in titanocenes, and titanocene hydrosulfide compounds [(C5Me4CH2Ph)(2)TiSH] (8) and [(C(5)Me(4)t-Bu)(2)TiSH] (9) by H2S-induced protonolysis of sigma-Ti-C bonds in [(eta(5)-C5Me4CH2Ph)Ti(III)(eta(5):eta(1)-C5Me4CH2-o-C6H4)] and [(C(5)Me(4)t-Bu)Ti(III)(eta(5):eta(1)-C5Me4CMe2CH2)], respectively. The crystal structures of 6, 8, and 9 and electronic absorption spectra of 6-9 in hexane solution highly resemble those of corresponding [Cp-2*Ti(SH)(2)] (1) and [Cp-2*TiSH] (2), however, compounds 6 and 7 strongly differ in their sensitivity to sunlight mutually and with respect to 1. The sunlight photolysis of 6 in toluene proceeded similarly to the process described previously for 1 except that about three times longer exposition (300 h) was required to obtain the cyclopentadienyltitanium sulfide cage cluster [{(C5Me4CH2Ph)Ti}(4)S-6] (10) in 48% yield. In contrast, compound 7 photo-decomposed very efficiently to give compound 9 as the only isolated titanium-containing product in 87% yield. The formation of 10 can be accounted for the redox elimination of the cyclopentadiene followed by elimination of hydrogen sulfide in intramolecular condensation reaction whereas the formation of 9 requires the dissociation of SH radicals. Both the processes were recognized by Rosenthal and Beweries to concur in photodecomposition of [Cp-2*Ti(OH)(2)]. New titanocene dihydrosulfide compounds [(C5Me4CH2Ph)(2)Ti(SH)(2)] (6) and [(C(5)Me(4)t-Bu)(2)Ti(SH)(2)] (7) were obtained by addition of hydrogen sulfide to the corresponding doubly tucked-in titanocenes, and titanocene hydrosulfide compounds [(C5Me4CH2Ph)(2)TiSH] (8) and [(C(5)Me(4)t-Bu)(2)TiSH] (9) by H2S-induced protonolysis of sigma-Ti-C bonds in [(eta(5)-C5Me4CH2Ph)Ti(III)(eta(5):eta(1)-C5Me4CH2-o-C6H4)] and [(C(5)Me(4)t-Bu)Ti(III)(eta(5):eta(1)-C5Me4CMe2CH2)], respectively. The crystal structures of 6, 8, and 9 and electronic absorption spectra of 6-9 in hexane solution highly resemble those of corresponding [Cp-2*Ti(SH)(2)] (1) and [Cp-2*TiSH] (2), however, compounds 6 and 7 strongly differ in their sensitivity to sunlight mutually and with respect to 1. The sunlight photolysis of 6 in toluene proceeded similarly to the process described previously for 1 except that about three times longer exposition (300 h) was required to obtain the cyclopentadienyltitanium sulfide cage cluster [{(C5Me4CH2Ph)Ti}(4)S-6] (10) in 48% yield. In contrast, compound 7 photo-decomposed very efficiently to give compound 9 as the only isolated titanium-containing product in 87% yield. The formation of 10 can be accounted for the redox elimination of the cyclopentadiene followed by elimination of hydrogen sulfide in intramolecular condensation reaction whereas the formation of 9 requires the dissociation of SH radicals. Both the processes were recognized by Rosenthal and Beweries to concur in photodecomposition of [Cp-2*Ti(OH)(2)].
dcterms:title
Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes
skos:prefLabel
Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes
skos:notation
RIV/00216208:11310/14:10272019!RIV15-MSM-11310___
n3:aktivita
n15:I n15:P n15:Z
n3:aktivity
I, P(GAP207/12/2368), P(GP203/09/P276), Z(MSM0021620857)
n3:cisloPeriodika
13
n3:dodaniDat
n10:2015
n3:domaciTvurceVysledku
n6:3157962 n6:5347440
n3:druhVysledku
n18:J
n3:duvernostUdaju
n21:S
n3:entitaPredkladatele
n16:predkladatel
n3:idSjednocenehoVysledku
47499
n3:idVysledku
RIV/00216208:11310/14:10272019
n3:jazykVysledku
n11:eng
n3:klicovaSlova
complexes; pi-donation; active catalysts; aromatic solvents; catalytic-hydrogenation; selective hydrogenation; unsaturated-hydrocarbons; frustrated Lewis pairs; spin-resonance spectra; titanium compounds (eta-5-c5me5)2tir
n3:klicoveSlovo
n8:frustrated%20Lewis%20pairs n8:active%20catalysts n8:catalytic-hydrogenation n8:unsaturated-hydrocarbons n8:selective%20hydrogenation n8:aromatic%20solvents n8:complexes n8:spin-resonance%20spectra n8:titanium%20compounds%20%28eta-5-c5me5%292tir n8:pi-donation
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[DB9BA36A8858]
n3:nazevZdroje
Organometallics
n3:obor
n12:CF
n3:pocetDomacichTvurcuVysledku
2
n3:pocetTvurcuVysledku
6
n3:projekt
n7:GAP207%2F12%2F2368 n7:GP203%2F09%2FP276
n3:rokUplatneniVysledku
n10:2014
n3:svazekPeriodika
33
n3:tvurceVysledku
Horáček, Michal Pinkas, Jiří Mach, Karel Kubišta, Jiří Císařová, Ivana Gyepes, Róbert
n3:wos
000339090700021
n3:zamer
n14:MSM0021620857
s:issn
0276-7333
s:numberOfPages
15
n4:doi
10.1021/om500296h
n19:organizacniJednotka
11310