Synthesis and Application of New Conductive Compounds Bearing Ferrocene and S-Heterocycles.

含二茂铁和S-杂环的新型导电化合物的合成及应用。

• 批准号: 15550158
• 负责人: IZUMI Taeko
• 金额: $ 2.05万
• 依托单位: YAMAGATA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550158/
• 关键词: Ferrocene ring; Tetrathiafulvalene(TTF); organic conductors; Thiophane ring; Electron donors; Charge-transfer(CT) complex

Two themes were investigated, (1)synthesis of new donor compounds which have tetrathiafulvalenes (TTFs) bearing ferrocene ring derived to conducting charge transfer (CT) complex ; (2)synthesis of thiophene oligomers bearing ferrocene ring.(1): As an example, 2-dimethoxy-phosphinyl-1,3-benzodithiole was prepared from anthranilic acid, then treatment of this phosphonate ester with ferrocenyl ketones (or phenyl keton as comparison) using the Wittig-Horner method in the presence of n-BuLi at-78 to 〜0℃ in dry THE afforded the donor compounds. New donor compounds which have ferrocene-TTFs bearing methyl, phenyl, hetero ring were synthesized by this way. The CT complexes were obtained from the reaction of the donor compounds with the well-known organic acceptor TCNQ or TCNQF_4 in CH_2Cl_2 at reflux temperature. The electrical conductivity measurement showed a substantial conductivity (σ = 0.26 S cm^<-1> ) when the case of 1,1'-disubstituted Ferrocene-TTFs-TCNQ compound.(2)3-Substituted thiophene derivatives which bind to ferrocene ring by triple or double bond were synthesized using palladium catalytic reaction. The cuppling reaction of 2-bromothiophene and thiophane was carried out using palladium catalyst. Oligomer compounds were obtained, but separation were not succeeded. Electrochemical properties were also examined for these compounds.

本论文主要研究了两个方面的问题：（1）以四硫富瓦烯（TTFs）为配体的二茂铁导电电荷转移（CT）配合物的合成;（2）含二茂铁噻吩低聚物的合成。(1)以邻氨基苯甲酸为原料合成了2-二甲氧基氧膦基-1，3-苯并二硫杂环戊烯，然后用Wittig-Horner法，在-78 ~100 ℃，正丁基锂存在下，与二茂铁酮（或苯酮）在干燥的THF中反应，得到给体化合物。用此方法合成了含二茂铁基的含甲基、苯基、杂环的TTFs的新型给体化合物。在CH_2Cl_2中，给体化合物与有机受体TCNQ或TCNQF_4在回流温度下反应，得到CT配合物。电导率测量显示当<-1>1，1 '-二取代的二茂铁-TTFs-TCNQ化合物的情况下具有显著的电导率（σ = 0.26S cm-3）。（2）利用钯催化反应合成了以三键或双键与二茂铁环连接的3-取代噻吩衍生物。以2-溴噻吩和噻吩硫番为原料，在钯催化剂作用下进行了杯合反应。得到了低聚物，但分离不成功。电化学性能也检查了这些化合物。

项目成果

Design and Synthesis of new Functional Compounds Related to Ferrocene bearing heterocyclic Moieties

带有杂环部分的二茂铁相关新型功能化合物的设计与合成

• 发表时间: 2003
• 期刊: Journal of Organometallic Chemistry 675
• 作者: A.A.O.Sarhan;A.A.O.Sarhan et al.;A.Sarhan;A.A.O.Sarhan
• 通讯作者: A.A.O.Sarhan

A.A.O.Sarhan, T.Izumi: "Design and synthesis of new functional compounds related to ferrocene bearing heterocyclic moieties"Journal of Organometallic Chemistry. 675. 1-12 (2003)

A.A.O.Sarhan、T.Izumi：“与带有杂环部分的二茂铁相关的新功能化合物的设计和合成”有机金属化学杂志。

A.Sarhan, T.Kijima, T.Izumi: "Synthesis and electrochemical properties of 1,1'-bis(benzo-1, 3-dithiol-2-yliden)ferrocene derivatives as novel electron donor compounds"Journal of Organometallic Chemistry. 682. 49-58 (2003)

A.Sarhan、T.Kijima、T.Izumi：“作为新型电子给体化合物的 1,1-双（苯并-1, 3-二硫醇-2-亚基）二茂铁衍生物的合成和电化学性能”有机金属化学杂志。

Synthesis and redox behavior of Novel benzo-1,3-dithiafulvalene Incorporating Ferrocene

新型苯并-1,3-二硫富瓦烯掺入二茂铁的合成及氧化还原行为

• 发表时间: 2004
• 期刊: Synthetic Metals 140(1)
• 作者: A.A.O.Sarhan

Synthesis and Redox Behavior of Novel Benzo-1,3-dithiafulvalenes Incorporating Ferrocene.

新型苯并-1,3-二硫富瓦烯掺入二茂铁的合成和氧化还原行为。

• 发表时间: 2004
• 期刊: Synthetic Metals 140(1)
• 作者: A.A.O.Sarhan;A.A.O.Sarhan et al.
• 通讯作者: A.A.O.Sarhan et al.