About: Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes     Goto   Sponge   NotDistinct   Permalink

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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)
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)
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)
skos:notation
  • RIV/00216208:11310/14:10272019!RIV15-MSM-11310___
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • I, P(GAP207/12/2368), P(GP203/09/P276), Z(MSM0021620857)
http://linked.open...iv/cisloPeriodika
  • 13
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 47499
http://linked.open...ai/riv/idVysledku
  • RIV/00216208:11310/14:10272019
http://linked.open...riv/jazykVysledku
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)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • US - Spojené státy americké
http://linked.open...ontrolniKodProRIV
  • [DB9BA36A8858]
http://linked.open...i/riv/nazevZdroje
  • Organometallics
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
http://linked.open...cetTvurcuVysledku
http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 33
http://linked.open...iv/tvurceVysledku
  • Císařová, Ivana
  • Mach, Karel
  • Pinkas, Jiří
  • Horáček, Michal
  • Kubišta, Jiří
  • Gyepes, Róbert
http://linked.open...ain/vavai/riv/wos
  • 000339090700021
http://linked.open...n/vavai/riv/zamer
issn
  • 0276-7333
number of pages
http://bibframe.org/vocab/doi
  • 10.1021/om500296h
http://localhost/t...ganizacniJednotka
  • 11310
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