テトラフルオロエチレンの選択的三量化反応の開発

四氟乙烯选择性三聚反应的进展

• 批准号: 19J12657
• 负责人: 村山 駿輝
• 金额: $ 1.34万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2019
• 资助国家: 日本
• 起止时间: 2019-04-25 至 2021-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19J12657/
• 关键词: テトラフルオロエチレン; オリゴマー化反応; メタラサイクル

本研究では，メタラサイクルを経るオレフィンのオリゴマー化反応をテトラフルオロエチレン(TFE)の選択的三量化に応用することを検討した．メタラサイクルを経るTFEの三量化反応において障壁となるのは，金属原子と2分子のTFEからなる五員環生成物が安定で，もう1分子のTFEの挿入が進行しないことである．五員環生成物の安定性は，金属からα炭素-フッ素結合の反結合性軌道への電子供与による強固な金属-α炭素結合に起因すると考えられる．五員環生成物の不安定化に向け金属上の電子密度を下げるため，当初は電子求引性のピンサー型錯体を用いる計画としていたが，計画を変更し，金属-α炭素結合を弱めるため，強いσ供与性部位を持つPBPピンサー型ロジウム錯体を用いて検討した．DFT計算により検討したところ，配位子のリン原子上にt-ブチル基を持つ場合は，1分子のTFEの配位のみが進行し，イソプロピル基を持つ場合は，五員環の形成が進行する可能性があるが，3分子目のTFEの配位の活性化障壁が高いことがわかった．一方，一級アルキル基を持つ場合では，3分子目のTFEの配位・挿入が進行し，七員環生成物を与える可能性があることがわかった．続いて，リン原子上にt-ブチル基・イソプロピル基を持つ錯体とTFEとの反応性を検討した．DFT計算により示唆された通り，t-ブチル基を持つ錯体の場合，1分子のTFEが配位した錯体が，イソプロピル基を持つ錯体の場合，ロジウム原子と2分子のTFEからなる五員環の生成が確認された．五員環生成物の構造は単結晶X線構造解析により同定された．以上の通り，TFEの三量化反応には至らなかったものの，過去に例のないピンサー型配位子を有する五員環生成物の合成および構造同定に成功した．またDFT計算においては，3分子のTFEと反応し七員環生成物を与え得る錯体群を見出した．

The purpose of this study is to determine the effectiveness of the three-quantification method selected by the TFE (TFE). The purpose of this study is to use the three-quantification method selected in this study. in this study, the results of this study are as follows: in this study, the results of this study are as follows: in this study, the results of this study are as follows: in this study, the results of this study are as follows: in this study, the results of this study are as follows: in this study, the results of this study are as follows: in this study, the results showed that the three-quantified products selected by the three-dimensional system were used in this study. in this study, the results of this study were analyzed in this study. The molecular weight of TFE is used for the determination of the stability of the five-member product, the combination of metal alpha carbon-carbon and metal alpha carbon. The cause of the combination of metal and metal strengthening metal-alpha carbon is tested. The instability of the five-member product leads to the reduction of the density of electrons on the metal. In the beginning, the computer used the computer program to design the device, the program was more accurate, the metal-alpha carbon was combined with the weak one, and the strong σ supply and the sexual position were used to maintain the PBP effect. the DFT calculation was used to calculate the performance of the device, and the coordination was carried out on the atom of the ligand. 1 molecular TFE coordination devices are in progress, and five members are responsible for the possibility of coordination, and the third subset of TFE coordination is highly active. On the one hand, the first level of coordination is stable, and the third subset of TFE is active. Seven-member products and possibilities do not cause significant changes. In this case, on the atom, there is a negative correlation between the wrong body and the TFE. The DFT calculation indicates that the wrong body is closed, the t-junction base holds the wrong body, the molecular TFE coordinates the wrong body, and the DFT calculation indicates that the wrong body is closed. In this paper, the atomic 2 molecular TFE is used to generate a confirmation device. The five-member product is used to analyze the crystal X-ray of the product, and to determine the same level of contact. the above information, TFEN three-quantitative reverse response to the production of electronic products In the past, there have been many cases in which five-member products have been successfully synthesized. DFT calculates that the products have been generated successfully, and that 3 molecules of TFE-based products have been generated from the wrong body group.