Zirconium compounds hydrolysis reactions

The thermochemistry of zirconium compounds has recently been the subject of a comprehensive critical review including data on the hydrolysis reactions (Brown, Curti and Grambow, 2005). In assessing the hydrolysis data, Brown et al. re-evaluated the existing data and derived a global model that was used... 

To examine the reactivity of the silyl-zirconium bond, Mori et al. used Me2PhSiLi instead of Ph2tBuSiLi. A THF solution of Me2PhSiLi 8b (1 equiv.) was added to a THF solution of Cp2ZrCl2 (1 equiv.) and diphenylacetylene 14a (1 equiv.) at -78 °C, and the solution was stirred at room temperature for 3 h. After hydrolysis of the reaction mixture, vinylsilane 15a was obtained in 36% yield along with the starting material 14a in 40% yield. When the reaction mixture was treated with D20, compound 15a-D2 having two deuteriums was obtained. One deuterium was introduced at the vinylic position and the other was incorporated into the methyl proton on the silicon (39% yield, each D content quant.). If insertion of alkyne 14a into the zirconium-carbon bond of lb occurs, vinylsilane 15a should be formed, but in this case only one deu-... 

A further complication concerning the involvement of water in the decomposition reactions has been reported for the decomposition of tertiary alkoxide compounds of zirconium. Kinetic studies on the decomposition of Zr(0-f-Bu)4 at 200-250°C showed that decomposition occurs by a chain reaction mechanism involving the hydrolysis of the zirconium alkoxide by water produced by the dehydration of the tertiary alcohol (Eq. 5.19 and 5.20) [129]. The dehydration of the tertiary alcohol is surface catalyzed, and the overall decomposition to Zr02 is given in Eq. 5.21. 

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