Creation of New pi-Electron Systems with Novel Properties and Functions

创建具有新特性和功能的新型 pi 电子系统

• 批准号: 04453027
• 负责人: IYODA Masahiko
• 金额: $ 4.54万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453027/
• 关键词: conductivity; Ferromagnetic interaction; donor; tetrathiafulvalene; ferrocene; palladium catalyzed reaction; cross-coupling; radical salt; 半導体; [3]ラジアレン; アフセプター; ジアニオン; CT錯体

In order to create the compounds which have both conductivity and ferromagnetic properties, we designed the donor systems bearing TTF- or ferrocene-unit at the 1,3-or 1,3,5-positions of aromatic rings. The donor molecules with TTF-units have been synthesized using the palladium-catalyzed cross-coupling reaction of tetrathiafulvalenyltin with halogenated benzene derivatives. The dication diradicals and trication triradicals prepared from the TTF-donors show conductivity like a semi-conductor. However, these radical salts indicate almost no ferromagnetic interaction between radical centers. The donor molecules with ferrocene-units have been synthesized by the palladium-catalyzed cross-coupling reaction of ferrocenylzinc reagent with halogenated benzene derivatives. This reaction easily produces the products in a one-pot procedure. The dication diradical or trication triradical salts of the ferrocenedonor show some interaction of ferrocenyl irons. However, the conductivity measurements of this system indicate that the radical salts are a insulator.

为了制备兼具导电性和铁磁性的化合物，我们设计了在芳环的1，3-或1，3，5-位上带有TTF-或二茂铁-单元的给体体系。利用钯催化的四硫富瓦烯锡与卤代苯衍生物的交叉偶联反应，合成了含TTF单元的给体分子。由TTF-施主制备的二价和三价自由基显示出半导体的导电性。然而，这些自由基盐表明自由基中心之间几乎没有铁磁相互作用。在钯催化下，二茂铁基锌试剂与卤代苯衍生物发生交叉偶联反应，合成了含二茂铁单元的给体分子。该反应在一锅法中容易地产生产物。二茂铁二酮的二价双自由基或三价三自由基盐显示出一定的二茂铁基离子相互作用。然而，该系统的电导率测量表明，自由基盐是绝缘体。

项目成果

Masahiko Iyoda: "Synthesis of (1,5-Diazabicyclo 4.3.0 nonan-2-ylidene-pentacarbonylchromium and -tungsten Using Reaction of Carbene Complexes with 6-Membered Hydrazine" Chem.Lett.777-778 (1994)

Masahiko Iyoda：“利用卡宾配合物与 6 元肼的反应合成 (1,5-二氮杂双环 4.3.0 壬基-2-亚基-五羰基铬和钨”Chem.Lett.777-778 (1994)

Hiroyuki Higuchi: "Synthesis of 1-(2,2-Dicuamoyimyl)-,1-(2,4,4-Tricyano-1,3-butadienyl)-,1,6-Bis(2,2-dicyanovinyl)-1,3,5-cycloheptatriene and Their Vinylogs" Bull.Chem.Soc.Jpn.66. 275-281 (1993)

Hiroyuki Higuchi：“1-(2,2-二氰基乙烯基)-,1-(2,4,4-三氰基-1,3-丁二烯基)-,1,6-双(2,2-二氰基乙烯基)-1的合成

Hideki Saitoh: "Crystal Structures of the Room-Temperature Phase of 4,4''-Difluoro-p-terphenyl and 4,4'''-Difluoro-p-quaterphenyl" Bull.Chem.Soc.Jpn.66. 2847-2853 (1993)

Hideki Saitoh：“4,4-二氟对三联苯和 4,4-二氟对四联苯的室温相的晶体结构”Bull.Chem.Soc.Jpn.66。

Masahiko Iyoda: "A Novel C=C Bond Cleavage in Hexacarbonyl(hexapentaene)diiron:X-Ray Crystal Structure of a Bis(μ_3,μ^2-allenylidene)-Iron Complex" J.Chem.Soc.,Chem.Commun.399-400 (1992)

Masahiko Iyoda：“六羰基（六戊烯）二铁中新型 C=C 键断裂：双（μ_3，μ^2-亚烯基）-铁络合物的 X 射线晶体结构”J.Chem.Soc.，Chem.Commun。 399-400 (1992)

Masahiko Iyoda, Li Zhao, and Haruo Matsuyama: ""Synthesis of (1,5-Diazabicyclo[4.3.0]nonan-2-ylidene)pentacarbonylchromium and -tungsten Using Reaction of 2-Unsaturated Carbene Complexes with 6-Membered Hydrazine"" Chem.Lett.777 (1994)

Masahiko Iyoda、Li Zhu 和 Haruo Matsuyama：“利用 2-不饱和卡宾配合物与 6 元肼的反应合成 (1,5-二氮杂双环[4.3.0]壬南-2-亚基)五羰基铬和钨”