Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain.

Result code in IS VaVaI

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Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain.

Original language description

Reduction of isomeric, fully-substituted titanocene dichlorides having a pendant double bond, [TiCl2(.eta.5-C5Me4R)(.eta.5-C5Me5)] (R = CH2CH2CH=CH2, 1; R = CH(Me)CH=CH2, 2), with magnesium in THF in the presence of bis(trimethylsilyl)ethyne (btmse) affords different products depending on the alkenyl chain length. Whereas the reduction of 1 yields a compound with intramolecularly .eta.2-coordinated double bond, [Ti(.eta.5-C5Me5)(.eta.2:.eta.5-C5Me4(CH2CH2CH=CH2)] (3), compound 2 affords under identicalconditions a product with two new Ti-C bonds, [Ti(.eta.1:.eta.1:.eta.5-C5Me3(CH2)(CH(Me)CH2CH2)}(.eta.5-C5Me5)] (4). The formation of 3 can be rationalized as a simple intramolecular stabilization of a titanocene intermediate formed by reductive removalof chloride ligands. The formation of 4 from the respective titanocene, however, requires formally an activation (oxidative addition) of one C-H bond at the methyl group adjacent to the unsaturated chain followed by a hydrogen shift.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2003

Confidentiality

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

Name of the periodical

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

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Volume of the periodical

667

Issue of the periodical within the volume

1/2

Country of publishing house

CH - SWITZERLAND

Number of pages

13

Pages from-to

154-166

UT code for WoS article

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EID of the result in the Scopus database

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