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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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; 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|
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