Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00492081" target="_blank" >RIV/61388955:_____/18:00492081 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/18:10381897
Result on the web
<a href="http://dx.doi.org/10.1039/c8dt01909f" target="_blank" >http://dx.doi.org/10.1039/c8dt01909f</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c8dt01909f" target="_blank" >10.1039/c8dt01909f</a>
Alternative languages
Result language
angličtina
Original language name
Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes
Original language description
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 waysnand, 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 andntemperature.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA17-13778S" target="_blank" >GA17-13778S: Aluminum free catalytic system utilizing hydrosilane-B(C6F5)3 adducts as activators in transition metal catalyzed ethylene polymerization</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
—
Volume of the periodical
47
Issue of the periodical within the volume
27
Country of publishing house
GB - UNITED KINGDOM
Number of pages
12
Pages from-to
8921-8932
UT code for WoS article
000444186100010
EID of the result in the Scopus database
2-s2.0-85049797030