Research on Synthesis and Aromaticity of Diaza [n] annulenes

本文研究了大环共轭二氮化合物(二氮杂轮烯)和乙烯键连接的八乙基卟啉(OEP)衍生物的合成，并用~1H核磁共振和电子吸收光谱考察了它们作为衡量二氮杂[n]环烯芳香性的抗磁环电流效应。首先，合成了多种二氮杂[n]轮烯衍生物，并考察了它们的芳香性，证明了氮原子的引入降低了与相应碳氢化合物相比的环电流。以二氮杂[n]轮烯为原料，合成了一种[11][13]富瓦烯衍生物，并用X-射线单晶衍射法对其芳香性进行了验证。然后，在催化剂存在下，进行了双氢[13]-和[15]-环酮的部分加氢反应。用…表征了它们的加氢产物的结构和性质基于分子力学(MM3)计算的优化几何构型，更是如此。此外，作为二氮杂[n]轮烯的组成起始原料的环烯酮被转化为相应的富烯并带有不同的取代基。其次，从不同的结构角度研究了八乙基卟啉(OEP)的芳香性。合成了乙烯桥联的双(OEP)-M和Tris(OEP)-M与d^8个过渡金属离子(M=Ni(II)、Pd(II)和Pt(II))的配合物。与OEP-M相比，(Z)-bi(OEP)-M的~1H核磁共振谱变化更大，而(E)-异构体的电子吸收谱变化更大。对基态的电子性质进行了研究，证明了tris(OEP)-M比bis(OEP)-M和Ni的络合物之间通过亚乙烯键的相互作用更强，而Ni的络合物则比Pd和Pt的络合物强。乙炔桥联的双、三(八乙基卟啉)S与d^8个过渡金属离子M(M1，M2，M3)：(Ni(II)，Pd(Li)，Pt(II))通过与M(TI)X盐的选择性金属化反应，合成了不同的乙烯桥双、三(八乙基卟啉)S的混合配合物。Tris(OEP)-(M1-M2-M3)的电子结构受较重金属的影响更大，导致Ni-Pd-Pt络合物的Soret带分裂最大。Tris(OEP)-(M1-M2-M3)的氧化电位E_t值表明，Ni-Pd-Pt络合物具有与Pd-Pd-Pd络合物几乎相同的电子释放能力。在双(OEP)-(M1-M2)的情况下，(E)-异构体的电子释放能力按重金属络合物的顺序呈现规律性的降低，而(Z)-异构体的电子释放能力几乎不依赖于所包含的金属。较少

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