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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)]. (en)
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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 (en)
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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 (en)
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skos:notation
| - RIV/00216208:11310/14:10272019!RIV15-MSM-11310___
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http://linked.open...avai/riv/aktivita
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http://linked.open...avai/riv/aktivity
| - I, P(GAP207/12/2368), P(GP203/09/P276), Z(MSM0021620857)
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http://linked.open...iv/cisloPeriodika
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http://linked.open...vai/riv/dodaniDat
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http://linked.open...aciTvurceVysledku
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http://linked.open.../riv/druhVysledku
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http://linked.open...iv/duvernostUdaju
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http://linked.open...titaPredkladatele
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http://linked.open...dnocenehoVysledku
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http://linked.open...ai/riv/idVysledku
| - RIV/00216208:11310/14:10272019
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http://linked.open...riv/jazykVysledku
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http://linked.open.../riv/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 (en)
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http://linked.open.../riv/klicoveSlovo
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http://linked.open...odStatuVydavatele
| - US - Spojené státy americké
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http://linked.open...ontrolniKodProRIV
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http://linked.open...i/riv/nazevZdroje
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http://linked.open...in/vavai/riv/obor
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http://linked.open...ichTvurcuVysledku
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http://linked.open...cetTvurcuVysledku
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http://linked.open...vavai/riv/projekt
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http://linked.open...UplatneniVysledku
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http://linked.open...v/svazekPeriodika
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http://linked.open...iv/tvurceVysledku
| - Císařová, Ivana
- Mach, Karel
- Pinkas, Jiří
- Horáček, Michal
- Kubišta, Jiří
- Gyepes, Róbert
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http://linked.open...ain/vavai/riv/wos
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http://linked.open...n/vavai/riv/zamer
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issn
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number of pages
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http://bibframe.org/vocab/doi
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http://localhost/t...ganizacniJednotka
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