Preparation and Reactions of Cationic Zirconacycles

阳离子锆环的制备与反应

• 批准号: 10640572
• 负责人: KOTORA Martin
• 金额: $ 2.05万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640572/
• 关键词: zirconium; dibutylzirconocene; cation species; zirconacycles; insertion; cyclization; methylalumoxane; ジルコニウム錯体; ジルコナシクロペンタジエン; カチオン錯体; 結合の活性化; シクロペンテノン; 選択的反応; カルボニレーション

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.

为了开发使用锆阳离子物种的新型反应，我们合成了用于该项目的新型锆络合物作为目标。当用二丁基二茂锆处理时，在C2碳上具有氯的二烯环化。在该反应中，二烯部分环化以形成作为环化产物的锆杂环戊烷。二烯C2位的氯原子进入锆环戊烷的β位。由于β-位上的氯离子的存在，进一步的反应得以进行。发生氯离子的消除，该部分转化为碳-碳双键，消除的氯离子被锆金属中心捕获。通过该反应得到烷基二茂锆氯化物。当化合物与甲基铝氧烷（MAO）和苯乙炔反应时，观察到了新型的插入反应。