Synthesis and Reactions of Cp*<sub>2</sub>Hf(η<sup>2</sup>-PhC<sub>2</sub>SiMe<sub>3</sub>) with Water and Carbon Dioxide
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The complexation of phenyl(trimethylsilyl)acetylene by decamethylhafnocene gave the complex Cp*2Hf(η2-PhC2SiMe3) (1-Hf). By comparison of detailed spectroscopic and structural data as well as of some regioselective reactions of 1-Hf to the titanium analogue Cp*2Ti(η2-PhC2SiMe3) (1-Ti) and the zirconium complex Cp*2Zr(η2-PhC2SiMe3) (1-Zr) one can try to understand how the metals interact in these complexes with differently substituted acetylenic carbon atoms. All data for 1-Hf show an extremely strong interaction of the alkyne with hafnium compared to the analogous compounds of titanium and zirconium. Complex 1-Hf reacted with water at the Hf−C(Ph) bond to form the complex Cp*2Hf(OH)−C(SiMe3)CHPh (2-Hf). With carbon dioxide, a mixture of regioisomeric hafnafuranones 4a/b-Hf was formed.
