Preparation and Reactions of Cationic Zirconacycles

为了开发利用锆阳离子的新型反应，我们合成了新型的锆配合物作为本项目的目标。在C2碳上有一个氯的二烯，当它们被二丁基锆新世处理时被环化。在该反应中，二烯部分环化形成锆环戊烷作为环化产物。二烯烃的C2碳上的氯来到锆环戊烷的β位。由于氯在β位置，反应继续进行。氯离子发生消去，这部分转化为碳碳双键，消去的氯离子被锆金属中心捕获。该反应可制得烷基二茂锆氯化物。用甲基铝氧烷和苯乙炔处理后，发现了新型的插入反应。

In order to develop novel type of reactions using zirconium cation species, we synthesized novel zirconium complexes which were used for the project as a target. Dienes which have a chloride at C2 carbon cyclized, when they were treated with dibutylzirconocene. In this reaction, the diene moiety cyclized to form a zirconacyclopentane as the cyclized product. The chloride at C2 carbon of dienes came to β-position of zirconacyclopentanes. And then further reaction proceeded because of the chloride at β-position. Elimination of the chloride occurred and this moiety was converted into a carbon-carbon double bond and the eliminated chloride was trapped by zirconium metal center. By this reaction alkylzirconocene chlorides were obtained. When the compounds were treated with MAO (methylalumoxane) and the phenylacetylene, novel type of insertion reaction was observed.