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.
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