Počet záznamů: 1  

Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes

  1. 1.
    SYSNO ASEP0492081
    Druh ASEPJ - Článek v odborném periodiku
    Zařazení RIVJ - Článek v odborném periodiku
    Poddruh JČlánek ve WOS
    NázevHydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes
    Tvůrce(i) Pinkas, Jiří (UFCH-W) RID, ORCID
    Gyepes, Robert (UFCH-W) RID, ORCID
    Císařová, I. (CZ)
    Kubišta, Jiří (UFCH-W) RID, ORCID
    Horáček, Michal (UFCH-W) RID, ORCID
    Žilková, Naděžda (UFCH-W) RID, ORCID
    Mach, Karel (UFCH-W) ORCID, RID
    Zdroj.dok.Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
    Roč. 47, č. 27 (2018), s. 8921-8932
    Poč.str.12 s.
    Jazyk dok.eng - angličtina
    Země vyd.GB - Velká Británie
    Klíč. slovaX-Ray structure ; carbon-monoxide ; acetylene complexes
    Vědní obor RIVCF - Fyzikální chemie a teoretická chemie
    Obor OECDPhysical chemistry
    CEPGA17-13778S GA ČR - Grantová agentura ČR
    Institucionální podporaUFCH-W - RVO:61388955
    UT WOS000444186100010
    EID SCOPUS85049797030
    DOI10.1039/c8dt01909f
    AnotaceReactions following the addition of dihydrogen under maximum atmospheric pressure to bis(trimethylsilyl) acetylene (BTMSA) complexes of titanocenes, [(η5-C5H5−nMen)2Ti(η2-BTMSA)] (n = 0, 1, 3, and 4) (1A–1D), and zirconocenes, [(η5-C5H5−nMen)2Zr(η2-BTMSA)] (n = 2–5) (4A–4D), proceeded in diverse ways
    and, depending on the metal, afforded different products. The former complexes lost, in all cases, their BTMSA ligand via its hydrogenation to bis-1,2-(trimethylsilyl)ethane when reacted at 80 °C for a prolonged reaction time. For n = 0, 1, and 3, the titanocene species formed in situ dimerised via the formation of fulvalene ligands and two bridging hydride ligands, giving known green dimeric titanocenes (2A–2C). For n = 4, a titanocene hydride [(η5-C5HMe4)2TiH] (2D) was formed, similarly to the known [(η5-C5Me5)2TiH] (2E) for n = 5. However, in contrast to this example, 2D in the absence of dihydrogen spontaneously dehydrogenated to the known Ti(III)–Ti(III) dehydro-dimer [{Ti(η5-C5HMe4)(μ-η1:η5-C5Me4)}2] (3B). This complex has now been fully characterised via spectroscopic methods, and was shown through EPR spectroscopy to attain an intramolecular electronic triplet state. The zirconocene-BTMSA complexes 4A–4D reacted uniformly with one hydrogen molecule to give Zr(IV) zirconocene hydride alkenyls, [(η5-C5H5−nMen)2ZrH{C(SiMe3)vCH(SiMe3)}] (n = 2–5) (5A–5D). These were identified through their 1H and 13C NMR spectra, which show features typical of an agostically bonded proton, vCH(SiMe3). Compounds 5A–5D formed equilibria with the BTMSA complexes 4A–4D depending on hydrogen pressure and
    temperature.
    PracovištěÚstav fyzikální chemie J.Heyrovského
    KontaktMichaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
    Rok sběru2019
Počet záznamů: 1  

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