Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/00216208:11310/18:10381897

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA17-13778S" target="_blank" >GA17-13778S: Hliník neobsahující katalytický systém využívající hydrosilan-B(C6F5)3 adukty jako aktivátory přechodných kovů při polymeraci ethylenu</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Svazek periodika

47

Číslo periodika v rámci svazku

27

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

8921-8932

Kód UT WoS článku

000444186100010

EID výsledku v databázi Scopus

2-s2.0-85049797030