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Statements

Subject Item
n2:RIV%2F00216208%3A11310%2F14%3A10272021%21RIV15-MSM-11310___
rdf:type
skos:Concept n14:Vysledek
rdfs:seeAlso
http://dx.doi.org/10.1016/j.jorganchem.2014.01.005
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
Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides
skos:prefLabel
Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides
skos:notation
RIV/00216208:11310/14:10272021!RIV15-MSM-11310___
n3:aktivita
n17:Z n17:I n17:P
n3:aktivity
I, P(GAP207/12/2368), P(GP203/09/P276), Z(MSM0021620857)
n3:cisloPeriodika
April
n3:dodaniDat
n4:2015
n3:domaciTvurceVysledku
n11:3157962
n3:druhVysledku
n6:J
n3:duvernostUdaju
n16:S
n3:entitaPredkladatele
n10:predkladatel
n3:idSjednocenehoVysledku
49064
n3:idVysledku
RIV/00216208:11310/14:10272021
n3:jazykVysledku
n5:eng
n3:klicovaSlova
crystal structure; sunlight; photolysis; hydrosulfide; titanocene; titanium
n3:klicoveSlovo
n13:crystal%20structure n13:titanocene n13:titanium n13:photolysis n13:hydrosulfide n13:sunlight
n3:kodStatuVydavatele
CH - Švýcarská konfederace
n3:kontrolniKodProRIV
[4E73DA503220]
n3:nazevZdroje
Journal of Organometallic Chemistry
n3:obor
n15:CF
n3:pocetDomacichTvurcuVysledku
1
n3:pocetTvurcuVysledku
7
n3:projekt
n20:GAP207%2F12%2F2368 n20:GP203%2F09%2FP276
n3:rokUplatneniVysledku
n4:2014
n3:svazekPeriodika
755
n3:tvurceVysledku
Lamač, Martin Kubišta, Jiří Císařová, Ivana Gyepes, Róbert Horáček, Michal Pinkas, Jiří Mach, Karel
n3:wos
000331191900019
n3:zamer
n19:MSM0021620857
s:issn
0022-328X
s:numberOfPages
10
n21:doi
10.1016/j.jorganchem.2014.01.005
n12:organizacniJednotka
11310