Yan Jiaying, Yang Yufeng, Ishida Masatoshi, Mori Shigeki, Zhang Bao, Feng Yaqing, Furuta Hiroyuki
Department of Chemistry and Biochemistry, Graduate School of Engineering, and Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395, Japan.
School of Chemical Engineering and Technology, Tianjin University and the Co-Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin, 300072, P.R. China.
Chemistry. 2017 Aug 22;23(47):11375-11384. doi: 10.1002/chem.201701958. Epub 2017 Jul 31.
Complexation of group 11 metal cations with an α-bis(phenylthio)-substituted trans-doubly N-confused porphyrin (trans-N CP : 4) afforded a series of square-planar trivalent organometallic complexes (i.e., Cu-H4, Ag-H4, and Au-H4). The X-ray crystal structures of the complexes revealed highly planar core geometries along with the presence of peripheral amine and imine nitrogen sites of the pyrrolic moieties. NMR, UV/Vis absorption, and magnetic circular dichroism (MCD) spectroscopies suggested the 18 π-electron aromaticity of the complexes. The aromaticity was also fully analyzed by various theoretical methodologies such as nucleus-independent chemical shift (NICS) and anisotropic induced current density (ACID) calculations. The central metal affects the amphiprotic character of the complexes possessing both pyrrolic amino nitrogen and imino nitrogen atoms at the periphery, which was examined by the photometric titration with trifluoroacetic acid (TFA) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. The inherent acidity of the complexes was followed in the order; Cu-H4>Au-H4>Ag-H4 and that of basicity was Au-H4>Ag-H4>Cu-H4. The complexes could be considered as an "expanded imidazole" structural motif.
第11族金属阳离子与α-双（苯硫基）取代的反式双N-稠合卟啉（反式-N CP：4）络合，得到了一系列平面四方三价有机金属络合物（即Cu-H4、Ag-H4和Au-H4）。这些络合物的X射线晶体结构显示出高度平面的核心几何结构，以及吡咯部分外围胺基和亚胺氮位点的存在。核磁共振、紫外/可见吸收和磁圆二色性（MCD）光谱表明这些络合物具有18π电子芳香性。芳香性也通过各种理论方法进行了全面分析，如核独立化学位移（NICS）和各向异性感应电流密度（ACID）计算。中心金属影响外围同时具有吡咯氨基氮和亚氨基氮原子的络合物的两性特征，分别通过用三氟乙酸（TFA）和1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）进行光度滴定来研究。络合物的固有酸度顺序为：Cu-H4>Au-H4>Ag-H4，碱性顺序为：Au-H4>Ag-H4>Cu-H4。这些络合物可被视为一种“扩展咪唑”结构单元。
