Počet záznamů: 1
Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes
- 1.
SYSNO ASEP 0492081 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Hydrogenation 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, RIDZdroj.dok. Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 47, č. 27 (2018), s. 8921-8932Poč.str. 12 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova X-Ray structure ; carbon-monoxide ; acetylene complexes Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA17-13778S GA ČR - Grantová agentura ČR Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000444186100010 EID SCOPUS 85049797030 DOI 10.1039/c8dt01909f Anotace Reactions 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.Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2019
Počet záznamů: 1