Research on Synthesis and Aromaticity of Diaza [n] annulenes

二氮杂[n]轮烯的合成及芳香性研究

• 批准号: 08454199
• 负责人: HIGUCHI Hiroyuki
• 金额: $ 2.3万
• 依托单位: Faculty of Science, Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454199/
• 关键词: diaza [18] annulene; aromaticity; diamagnetic ring current; porphyrin; complex; metalation; ^1H NMR spectra; electronic absorption spectra; アヌレンジオン; ジオキシム; diatropicity; カップリング; 結合交替; ジカチオン; 非極在化; 大環状共役化合物; 非局在化; 共役

Studies on the syntheses of the macrocyclic conjugated diaza compounds (diazaannulenes) as well as the octaethylporphyrin (OEP) derivatives connected with the vinylene-linkage were carried out and also on their diamagnetic ring current effects as a measure of aromaticity of diaza[n]annulenes were examined by means of ^1H NMR and electronic absorption spectra. Firstly, a variety of diaza[n]annulene derivatives was synthesized and examined their aromatic properties, proving that incorporation of nitrogen atom into the pi-electronic conjugation system reduces their ring currents as compared with those of the corresponding hydrocarbons. In relation with diaza[n]annulenes, an [11][13] fulvalene derivative has been successfully synthesized and verified its aromaticity also based on X-ray crystallography. Then, partial hydrogenations of bisdehydro[13]- and [15]annulenones were carried out in the presence of catalyses. Structures and tropicities of their hydrogenation products were examined al … More so based on the optimized geometries by means of molecular mechanics (MM3) calucalations. Furthermore, annuleneones as the constituent starting meterials for diaza[n]annulenes were transformed to the corresponding fulvenes bearing various substituents. Their tropicities were examined and compared with those of the known compounds.Secondly, aromaticity of octaethylporphyrin (OEP) was studied from various structural viewpoints. Complexes of vinylene-bridged bis(OEP)-M and tris(OEP)-M with d^8 transition-metal ions (M=Ni(II), Pd(II), and Pt(II)) were synthesized. ^1H NMR spectra varied more drastically for (Z)-bis(OEP)-M, with respect to those of OEP-M, while electronic absorption spectra for (E)-isomers. Electronic properties at the ground state were examined, proving that the interaction between the constituent QEP rings through the vinylene-linkages is more intensive for tris(OEP)-M than for bis(OEP)-M and yet for the Ni complex than for the Pd and Pt ones. Various mixed complexes of vinylene-bridged bis- and tris(octaethylporphyrin)s (bis(OEP)-(M I-M2) and tris(OEP)-(M1-M2-M3)) with d^8 transition-metal ions M ((M1, M2, M3) : (Ni(II), Pd(lI), Pt(II)) were also synthesized by selective metalations of the corresponding free-bases with M(TI)X salts. Electronic structures of tris(OEP)-(M1-M2-M3) proved to be affected by the heavier metals more intensively, resulting in the largest splitting of Soret band for the Ni-Pd-Pt complex. Oxidation potential E_t values of tris(OEP)-(M1-M2-M3) suggested that the Ni-Pd-Pt complex possesses the electron-releasing ability almost the same as the Pd-Pd-Pd one. In the case of bis(OEP)-(M1-M2), the (E)-isomers exhibited the reduction of electron-releasing ability regularly in order of the heavier metal complexes, while the (Z)-isomers exhibited little dependency of the electron-releasing ability upon the incorporated metals. Less

研究了大环共轭双氮环烯化合物（diazaannulenes）的合成以及乙烯链连接的辛乙基卟啉（octaethylporphyrin， OEP）衍生物的合成，并利用^1H NMR和电子吸收光谱检测了作为双氮环烯芳香性指标的抗磁环电流效应。首先，合成了多种双氮[n]环烯衍生物，并对其芳香性质进行了测试，证明了在pi-电子共轭体系中加入氮原子比相应的碳氢化合物减少了环电流。与杂[n]环烯相关，成功合成了[11][13]fulvalene衍生物，并通过x射线晶体学验证了其芳香性。然后，在催化剂的存在下，对双脱氢[13]-和[15]环烯酮进行了部分加氢反应。通过分子力学（MM3）计算，对优化后的加氢产物的结构和热向性进行了分析。此外，环烯酮作为双氮环烯的组成原料转化为相应的含不同取代基的杂环烯。研究了它们的趋向性，并与已知化合物的趋向性进行了比较。其次，从不同的结构角度研究了八乙基卟啉（OEP）的芳构性。合成了乙烯桥接的二(OEP)-M和三(OEP)-M与d^8过渡金属离子（M=Ni（II）、Pd（II）和Pt(II)）配合物。^与OEP-M相比，(Z)-bis(OEP)-M的1H NMR谱变化更大，而(E)-异构体的电子吸收谱变化更大。研究了基态的电子性质，证明了QEP环通过乙烯键的相互作用在tris(OEP)-M中比在bis(OEP)-M中更强烈，而在Ni配合物中比在Pd和Pt配合物中更强烈。通过与M(TI)X盐选择性地金属化相应的自由碱，合成了乙烯桥接的双-和三（八乙基卟啉）s (bis(OEP)-(M I-M2)和tris（OEP)-(M1-M2-M3)）与d^8过渡金属离子M((M1, M2, M3): (Ni(II), Pd（lI), Pt(II)）的混合配合物。tris(OEP)-(M1-M2-M3)的电子结构受重金属的影响更大，导致Ni-Pd-Pt配合物的Soret带分裂最大。tris(OEP)-(M1-M2-M3)的氧化电位E_t值表明，Ni-Pd-Pt配合物具有与Pd-Pd-Pd几乎相同的电子释放能力。在bis(OEP)-(M1-M2)的情况下，(E)-异构体的电子释放能力按照重金属配合物的顺序有规律地降低，而(Z)-异构体的电子释放能力对加入金属的依赖性较小。少

项目成果

H.Higuchi: "Mono-, Di-, and Trimetallic Palladium (II) Porphyrin Trimers with Etheno-bridges" Chem.Lett.593-594 (1996)

H.Higuchi：“具有乙烯桥的单金属、二金属和三金属钯 (II) 卟啉三聚体”Chem.Lett.593-594 (1996)

H.Higuchi: "5,10-Dimethyl[13]annulenone, the First Monocyclic Annulenone Larger Than Tropone" Tetrahedron Lett.37. 2601-2604 (1996)

H.Higuchi：“5,10-二甲基[13]轮环酮，第一个比托酮更大的单环轮环酮”四面体快报.37。

H.Higuchi: "Huckel Rule" Kagaku. 53 (9). 53-55 (1998)

H.Higuchi：“休克尔规则” Kagaku。

Higuchi,H.他: "Synthesis and Properties of Unsymmetrically Substituted Bi-and Quaterthiophenes" Bull.Chem.Soc.Jpn.71. 483-495 (1998)

Higuchi, H. 等人：“不对称取代的双噻吩和四噻吩的合成和性质”Bull.Chem.Soc.Jpn.71 (1998)。

H.Higuchi: "Synthesis and Electronic Absorption Spectra of Orientational Isomers of Bithiophene Derivatives Bridged with 1,3-Butadiene Linkages" Mol.Cryst.Liq.Cryst.Sci.Technol.Sec.B. (印刷中).

H. Higuchi：“用 1,3-丁二烯键桥连的联噻吩衍生物的定向异构体的合成和电子吸收光谱”Mol.Cryst.Liq.Cryst.Sci.Technol.Sec.B。