About: Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization     Goto   Sponge   NotDistinct   Permalink

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  • The efficient catalytic dehydropolymerization of phenylsilane by homogeneous zirconocene bissilanolates ([{(c-C5H9)(7)Si8O12O}(2)Zr(eta(5)-C5H5)(2)] (1a); [{(c-C5H9)(7)Si8O12O}(2)Zr(eta(5)-C5H4Bu)(2)] (1b) [{(c-C5H9)(7)Si7O9(OSiMe3)O-2}Zr(eta(5)-C5H5)(2)] (4); [{(Me3CO)(3)SiO}(2)Zr(eta(5)-C5H5)(2)] (5)) and chlorosilanolates ([{(c-C5H9)(7)Si8O12O}ZrCl(eta(5)-C5H4Bu)(2)] (2); ([{(c-C5H9)(7)Si7O9O3}Zr2Cl(eta(5)-C5H5)(4)] (3a); [{(c-C5H9)(7)Si7O9O3}Zr2Cl(eta(5)-C5H4Bu)(4)] (3b)) has been demonstrated. The presence of at least one silanol ligand in the zirconocene moiety was found essential for high catalytic performance. Solid state structure of complex 1a was determined by single crystal X-ray diffraction analysis. A series of nine zirconocene-siliceous catalysts were prepared by grafting of zirconocene moiety onto silica using three general methods: (a) reaction of [(eta(5)-C5H5)(2)ZrCl2] with silica in the presence of NEt3; (b) reaction of [(eta 5-C5H5)(2)ZrMe2] with silica; (c) reaction of solely [(eta(5)-C5H5)(2)ZrCl2] with silica. Supported catalysts were characterized by ICP-MS, FT-IR, TGA and selected examples by XPS analysis. Those catalysts prepared by method (a) and (b) were found efficient in the phenylsilane polymerization although a higher Zr/monomer ratio had to be used in comparison with homogeneous analogues. The low concentration of residual silanol groups in supported catalysts was found essential for their high catalytic performance. Advantageous reusability of supported catalysts was demonstrated using SiO2(500)/Cp2ZrCl2/NEt3(5.8). The catalytic performance was retained in three consecutive cycles producing polymers with almost identical properties.
  • The efficient catalytic dehydropolymerization of phenylsilane by homogeneous zirconocene bissilanolates ([{(c-C5H9)(7)Si8O12O}(2)Zr(eta(5)-C5H5)(2)] (1a); [{(c-C5H9)(7)Si8O12O}(2)Zr(eta(5)-C5H4Bu)(2)] (1b) [{(c-C5H9)(7)Si7O9(OSiMe3)O-2}Zr(eta(5)-C5H5)(2)] (4); [{(Me3CO)(3)SiO}(2)Zr(eta(5)-C5H5)(2)] (5)) and chlorosilanolates ([{(c-C5H9)(7)Si8O12O}ZrCl(eta(5)-C5H4Bu)(2)] (2); ([{(c-C5H9)(7)Si7O9O3}Zr2Cl(eta(5)-C5H5)(4)] (3a); [{(c-C5H9)(7)Si7O9O3}Zr2Cl(eta(5)-C5H4Bu)(4)] (3b)) has been demonstrated. The presence of at least one silanol ligand in the zirconocene moiety was found essential for high catalytic performance. Solid state structure of complex 1a was determined by single crystal X-ray diffraction analysis. A series of nine zirconocene-siliceous catalysts were prepared by grafting of zirconocene moiety onto silica using three general methods: (a) reaction of [(eta(5)-C5H5)(2)ZrCl2] with silica in the presence of NEt3; (b) reaction of [(eta 5-C5H5)(2)ZrMe2] with silica; (c) reaction of solely [(eta(5)-C5H5)(2)ZrCl2] with silica. Supported catalysts were characterized by ICP-MS, FT-IR, TGA and selected examples by XPS analysis. Those catalysts prepared by method (a) and (b) were found efficient in the phenylsilane polymerization although a higher Zr/monomer ratio had to be used in comparison with homogeneous analogues. The low concentration of residual silanol groups in supported catalysts was found essential for their high catalytic performance. Advantageous reusability of supported catalysts was demonstrated using SiO2(500)/Cp2ZrCl2/NEt3(5.8). The catalytic performance was retained in three consecutive cycles producing polymers with almost identical properties. (en)
Title
  • Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization
  • Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization (en)
skos:prefLabel
  • Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization
  • Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization (en)
skos:notation
  • RIV/67985858:_____/12:00375909!RIV13-GA0-67985858
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • I, N, P(GA203/09/1574), P(KAN100400701), V, Z(AV0Z40400503), Z(AV0Z40720504), Z(MSM0021620857)
http://linked.open...iv/cisloPeriodika
  • 1
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
  • 182380
http://linked.open...ai/riv/idVysledku
  • RIV/67985858:_____/12:00375909
http://linked.open...riv/jazykVysledku
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  • catalysis; dehydrocoupling; polysilanes (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • NL - Nizozemsko
http://linked.open...ontrolniKodProRIV
  • [60EEA60EFB7A]
http://linked.open...i/riv/nazevZdroje
  • Catalysis Today
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
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http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 179
http://linked.open...iv/tvurceVysledku
  • Císařová, I.
  • Pinkas, Jiří
  • Sýkora, Jan
  • Horáček, Michal
  • Bastl, Zdeněk
  • Merna, J.
  • Varga, V.
http://linked.open...ain/vavai/riv/wos
  • 000298404600016
http://linked.open...n/vavai/riv/zamer
issn
  • 0920-5861
number of pages
http://bibframe.org/vocab/doi
  • 10.1016/j.cattod.2011.07.006
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