Lin Xiao-Tao, Ishizaka Yusuke, Maegawa Yoshifumi, Takeuchi Katsuhiko, Inagaki Shinji, Matsumoto Kazuhiro, Choi Jun-Chul
National Institute of Advanced Industrial Science and Technology (AIST) Tsukuba Central 5, 1-1-1 Higashi Tsukuba Ibaraki 305-8565 Japan
Graduate School of Pure and Applied Sciences, University of Tsukuba 1-1-1 Tennodai Tsukuba Ibaraki 305-8573 Japan.
RSC Adv. 2023 Mar 9;13(12):7828-7833. doi: 10.1039/d2ra08272a. eCollection 2023 Mar 8.
1,10-Phenanthroline (Phen) is a typical ligand for metal complexation and various metal/Phen complexes have been applied as a catalyst in several organic transformations. This study reports the synthesis of a Phen-based periodic mesoporous organosilica (Phen-PMO) with the Phen moieties being directly incorporated into the organosilica framework. The Phen-PMO precursor, 3,8-bis[(triisopropoxysilyl)methyl]-1,10-phenanthroline (1a), was prepared the Kumada-Tamao-Corriu cross-coupling of 3,8-dibromo-1,10-phenanthroline and [(triisopropoxysilyl)methyl]magnesium chloride. The co-condensation of 1a and 1,2-bis(triethoxysilyl)ethane in the presence of P123 as the template surfactant afforded Phen-PMO 3 with an ordered 2-D hexagonal mesoporous structure as confirmed by nitrogen adsorption/desorption measurements, X-ray diffraction, and transition electron microscopy. Co(OAc) was immobilized on Phen-PMO 3, and the obtained complex showed good catalytic activity for the hydrosilylation reaction of phenylacetylene with phenylsilane.
1,10-菲咯啉（Phen）是一种典型的金属络合配体，多种金属/Phen络合物已被用作多种有机转化反应的催化剂。本研究报道了一种基于菲咯啉的周期性介孔有机硅（Phen-PMO）的合成，其中菲咯啉部分直接掺入有机硅骨架中。通过3,8-二溴-1,10-菲咯啉与[(三异丙氧基甲硅烷基)甲基]氯化镁的熊田-玉尾-古里乌交叉偶联反应制备了Phen-PMO前体3,8-双[(三异丙氧基甲硅烷基)甲基]-1,10-菲咯啉（1a）。在作为模板表面活性剂的P123存在下，1a与1,2-双（三乙氧基甲硅烷基）乙烷的共缩合反应得到了具有有序二维六方介孔结构的Phen-PMO 3，这通过氮气吸附/脱附测量、X射线衍射和透射电子显微镜得到证实。将醋酸钴固定在Phen-PMO 3上，所得络合物对苯乙炔与苯基硅烷的硅氢化反应显示出良好的催化活性。
