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Tandem Si-C and C-H activation for decamethylhafnocene and bis(trimethylsilyl) acetylene

Beweries, Torsten and Burlakov, Vladimir V and Bach, Marc A and Peitz, Stephan and Arndt, Perdita and Baumann, Wolfgang and Spannenberg, Anke and Rosenthal, Uwe and Pathak, Biswarup and Jemmis, Eluvathingal D (2007) Tandem Si-C and C-H activation for decamethylhafnocene and bis(trimethylsilyl) acetylene. In: Angewandte Chemie International Edition, 46 (36). pp. 6907-6910.

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Abstract

The unusual reactivity of hafnocene complexes in comparison to their titanium and zirconium analogues was dramatically demonstrated in the recent functionalization of coordinated $N_2$ and the coupling of $CO_2$ and $N_2$ to a substituted hydrazine product;[1,2] The differences in their structure and bonding were also noticed;[3] for example,the \sigma and \pi ratio of the diene bonding in $(s-cis-\eta^4-diene)$ metallocene complexes is shifted to larger \sigma character for Hf compared to Zr,thus giving shorter Hf-C than Zr-C bonds. Herein,we report the unusual tandem Si-C and C-H bond activation of decamethylhafnocene and bis(trimethylsilyl)acetylene,which could not be carried out using titanium and zirconium congeners.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to John Wiley & Sons, Inc.
Keywords: CH activation;density functional calculations;hafnium;metallacycles;SiC activation.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 05 Aug 2008
Last Modified: 19 Sep 2010 04:48
URI: http://eprints.iisc.ernet.in/id/eprint/15451

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