DEVELOPMENT OF NEW CATALYSIS REACTIONS WITH METAL SALTS OF FLUORINATED WEAKLY COORDINATED ANIONS

含氟弱配位阴离子金属盐新催化反应的开发

• 批准号: 12640572
• 负责人: SONODA Takaaki
• 金额: $ 2.3万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640572/
• 关键词: FLUORINATED WEAKLY COORDINATED ANIONS; LEWIS ACIDITY OF LITHIUM IONS; HALOCHROMISM; DIELS-ALDER REACTIONS PROMOTED BY LITHIUM IONS; VALENCE-ISOMERIZATION OF QUADRICYCLANE; STRUCTURE-REACTIVITY RELATIONSHIP; ab initio calculations; DFT methods

THIS IS A BASIC RESEARCH TO PREPARE ALKALI METAL AND ALKALI-EARTH METAL SALTS OF VARIOUS FLUORINATED WEAKLY COORDINATING ANIONS AND TO INVESTIGATE SOME NEW CARBON-CARBON BOND FORMATION REACTIONS WHICH CAN BE PROMOTED IN CATALYTIC WAYS BY ELECTROPHILIC LITHIUM IONS EXTREMELY ACTIVATED BY THE COUNTER ANIONS IN WEAKLY COORDINATING ORGANIC SOLVENTS. THE EFFECTS OF METAL IONS AND THE STRUCTURE OF WEAKLY COORDINATING ANIONS ON THE CATALYTIC ACTIVITY AND THE MECHANISM OF THE REACTIONS ARE INVESTIGATED BY EXPERIMENTAL AND COMPUTATIONAL METHODS.COMPUTATIONAL STUDY: THE COORDINATING ABILITY OF VARIOUS WEAKLY COORDINATING ANIONS WAS QUANTITATIVELY EVALUATED AS FOLLOWS BY GAUSSIAN 98 AND SPARTAN WITH AB INITIO AND DFT METHODS; 1) THE RELATIONSHIP BETWEEN GAS-PHASE ACIDITY AND CALCULATED ACIDITY OF NEUTRAL BROENSTED-TYPE SUPERACIDS; 2) THE EFFECT OF COUNTER ANIONS ON THE ELECTROPHILICITY OF LITHIUM IONS TOWARD VARIOUS ORGANIC COMPOUNDS; 3) TRANSITION STATE STRUCTURES OF DIELS -ALDER REACTION AND VALENCE- ISOMERIZATION OF QUADRICYCLANE PROMOTED BY LITHIUM IONS.EXPERIMENTAL STUDY: VARIOUS/LITHIUM AND SODIUM SALTS OF FLUORINATED WEAKLY COORDINATING ANIONS SUCH AS TETRAARYLBORATE ANIONS, IMIDE ANIONS, METHIDE ANIONS, AND ALUMINATE ANIONS ARE NEWLY PREPARED. HALOCHROMIZM OF TRITYL CHLORIDE AND TRITYL ALCOHOLE AND DIELS-ALDER REACTIONS OF CYCLOPENTADIENE AND VALENCE- ISOMERIZATION REACTIONS OF QUADRICYCLANE PRPMOTED BY VARIOUS LITHIUM SALTS IN WEAKLY COORDINATING ORGANIC SOLVENTS ARE INVESTIGATED BY KINETIC METHODS TO EVALUATE THE LEWIS ACIDITY OF LITHIUM IONS IN SOLUTION.

这是一项基础研究，旨在制备各种氟化弱配位阴离子的碱金属和碱土金属盐，并研究一些可以通过亲电锂离子催化方式促进的新的碳-碳键形成反应。在弱配位有机溶剂中被反阴离子极度激活。通过实验和计算方法研究了金属离子和弱配位阴离子的结构对催化活性和反应机理的影响。计算研究：各种弱配位阴离子的配位能力采用从头算起和DFT方法对Gaussian 98和SPARTAN进行了如下定量评估； 1) 中性布朗斯特型超酸的气相酸度与计算酸度之间的关系； 2) 抗衡阴离子对锂离子对各种有机化合物的亲电性的影响； 3) 锂离子促进的四环烷的狄尔斯-阿尔德反应和价态异构化的过渡态结构。实验研究：氟化弱配位阴离子如四芳基硼酸阴离子、酰亚胺的各种/锂盐和钠盐阴离子、甲基阴离子和铝酸盐阴离子是新制备的。动力学研究了弱配位有机溶剂中三苯甲基氯和三苯甲基醇的卤代反应以及各种锂盐促进的环戊二烯的狄尔斯-阿尔德反应和四环烷的价态异构化反应评估溶液中锂离子路易斯酸度的方法。

项目成果

Kanji Fujiki, et al.: "Syntheses of Lipophilic Tetraarylborate Ions Substituted with Many Perfluoroalkyl Groups and Their Stability under Acid Conditions"Journal of Fluorine Chemistry. 102. 293-300 (2000)

Kanji Fujiki等人：“被许多全氟烷基取代的亲脂性四芳基硼酸根离子的合成及其在酸性条件下的稳定性”氟化学杂志。

Kanji Fujiki,Junji,Ichikawa,Hiroshi,Kobayashi,Akinari,Sonoda,Takaaki Sonoda: "Syntheses of Lipophilic Tetraarylborate Ions Substituted with Many Perfluoroallkyl Groups and Their Stability under Acid Conditions"Journal of Fluorine Chemistry. 102. 293-300 (

Kanji Fujiki、Junji、Ichikawa、Hiroshi、Kobayashi、Akinari、Sonoda、Takaaki Sonoda：“被许多全氟烷基取代的亲脂性四芳基硼酸根离子的合成及其在酸性条件下的稳定性”氟化学杂志。

Kanji Fujiki,Shin-ya,Ikeda,Hiroshi,Kobayashi,Akira Mori,Akira Nagira,Jin Nie,Takaaki Sonoda,Yurii A.Yagupolskii: "Evaluation of Lewis Acidity of "Naked"Lithium Ion Through Diels-Alder Reaction Catalyzed by Lithium TFPB in Nonpolar Organic Solvents"Chemist

Kanji Fujiki,Shin-ya,Ikeda,Hiroshi,Kobayashi,Akira Mori,Akira Nagira,Jin Nie,Takaaki Sonoda,Yurii A.Yagupolskii：“通过锂 TFPB 催化的 Diels-Alder 反应评估“裸”锂离子的路易斯酸度

池田 慎哉, 園田 高明, 森 章: "リチウムイオンによって加速されたクアドリシクランからノルボルナジェンへの原子化異性化反応"九州大学機能物質科学研究所報告. 15・2. 177-181 (2001)

池田慎哉、园田隆明、森明：“锂离子加速四环烷向降冰片二烯的雾化异构化反应”九州大学功能材料科学研究所报告15・2（2001）。

池田慎哉 その他: "トリチルカチオン生成反応に及ぼすリチウムイオンの求電子反応性の定量化"九州大学機能物質科学研究所報告. 15・2. 169-175 (2001)

池田真也等：“三苯甲基阳离子生成反应中锂离子的亲电反应性的定量”九州大学功能材料科学研究所报告15・2（2001）。