Reactivity of Titanocene Pendant Si-H Group towards Alcohols. Unexpected Formation of Siloxanes from the Reaction of Hydrosilanes and Ph3COH Catalyzed by B(C6F5)3

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F13%3A00394704" target="_blank" >RIV/61388955:_____/13:00394704 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/67985858:_____/13:00394704

Výsledek na webu

<a href="http://dx.doi.org/10.1021/om400253g" target="_blank" >http://dx.doi.org/10.1021/om400253g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/om400253g" target="_blank" >10.1021/om400253g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reactivity of Titanocene Pendant Si-H Group towards Alcohols. Unexpected Formation of Siloxanes from the Reaction of Hydrosilanes and Ph3COH Catalyzed by B(C6F5)3

Popis výsledku v původním jazyce

The reaction of [Cp(?5-C5H4CH2SiMe2H)- TiCl2] (1; Cp = ?5-C5H5) and methanol in the presence of catalytic amounts of B(C6F5)3 afforded a complex with a pendant silyl ether group, [Cp(?5-C5H4CH2SiMe2OMe)- TiCl2] (2), in good yield. The analogous reactionof 1 and Ph3COH resulted in the unexpected formation of [CpTiCl2{?-?5:?5-(C5H4)CH2SiMe2OSiMe2CH2(C5H4)}TiCl2Cp] (4). The formation of siloxanes from the reaction of 2 equiv of hydrosilane with Ph3COH mediated by B(C6F5)3 has a general applicability and proceeds in two consecutive steps: (i) transfer of the hydroxyl group from the trityl moiety to the silicon atom and (ii) silylation of the silanol formed in situ with the second equivalent of hydrosilane. The different hydrosilane reactivity toward Ph3COH in comparison with other alcohols can be attributed to the easy generation of the borate salt [Ph3C]+[(C6F5)3B(?-OH)B(C6F5)3] (5) under catalytic conditions. The intramolecular SiH and TiCl exchange in 1 is catalyzed by B(C6F5)3 in the

Název v anglickém jazyce

Reactivity of Titanocene Pendant Si-H Group towards Alcohols. Unexpected Formation of Siloxanes from the Reaction of Hydrosilanes and Ph3COH Catalyzed by B(C6F5)3

Popis výsledku anglicky

The reaction of [Cp(?5-C5H4CH2SiMe2H)- TiCl2] (1; Cp = ?5-C5H5) and methanol in the presence of catalytic amounts of B(C6F5)3 afforded a complex with a pendant silyl ether group, [Cp(?5-C5H4CH2SiMe2OMe)- TiCl2] (2), in good yield. The analogous reactionof 1 and Ph3COH resulted in the unexpected formation of [CpTiCl2{?-?5:?5-(C5H4)CH2SiMe2OSiMe2CH2(C5H4)}TiCl2Cp] (4). The formation of siloxanes from the reaction of 2 equiv of hydrosilane with Ph3COH mediated by B(C6F5)3 has a general applicability and proceeds in two consecutive steps: (i) transfer of the hydroxyl group from the trityl moiety to the silicon atom and (ii) silylation of the silanol formed in situ with the second equivalent of hydrosilane. The different hydrosilane reactivity toward Ph3COH in comparison with other alcohols can be attributed to the easy generation of the borate salt [Ph3C]+[(C6F5)3B(?-OH)B(C6F5)3] (5) under catalytic conditions. The intramolecular SiH and TiCl exchange in 1 is catalyzed by B(C6F5)3 in the

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2013

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

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Svazek periodika

32

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

4122-4129

Kód UT WoS článku

000323143400014

EID výsledku v databázi Scopus

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