类太空飞行器的八核钴(II)-硅倍半氧烷纳米笼：合成、结构、磁性、溶液行为及对酮的硼氢化反应的催化活性。

Space Craft-like Octanuclear Co(II)-Silsesquioxane Nanocages: Synthesis, Structure, Magnetic Properties, Solution Behavior, and Catalytic Activity for Hydroboration of Ketones.

机构信息

Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials , Shandong University , Jinan , 250100 , People's Republic of China.

State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen , 361005 , People's Republic of China.

出版信息

Inorg Chem. 2019 Apr 1;58(7):4574-4582. doi: 10.1021/acs.inorgchem.9b00137. Epub 2019 Mar 19.

DOI:10.1021/acs.inorgchem.9b00137

PMID:30887809

Abstract

Two novel space craft-like octanuclear Co(II)-silsesquioxane nanocages, {Co(MeSiO)} (SD/Co8a) and {Co(PhSiO)} (SD/Co8b) (SD = SunDi; Hdmpz = 3,5-dimethylpyrazole), have been constructed from two similar multidentate silsesquioxane ligands assisted with a pyrazole ligand. The Co skeleton consists of eight tetrahedral Co(II) ions arranged in a ring and is further capped by two (MeSiO) ligands up and down. The auxiliary dmpz ligands seal the ring finally. Electrospray ionization mass spectrometry revealed SD/Co8a and SD/Co8b are highly stable in CHCl. Magnetic analysis implies that SD/Co8a announces antiferromagnetic interactions between Co(II) ions. Moreover, both of them display good homogeneous catalytic activity for hydroboration of ketones in the presence of pinacolborane under mild conditions.

摘要

两个新颖的类飞船式八核钴（II）-硅倍半氧烷纳米笼，{Co(MeSiO)}（SD/Co8a）和{Co(PhSiO)}（SD/Co8b）（SD = SunDi；Hdmpz = 3,5-二甲基吡唑），由两个类似的多齿硅倍半氧烷配体和一个吡唑配体构建而成。Co 骨架由八个四面体 Co(II)离子组成，排列成一个环，进一步由上下两个（MeSiO）配体封端。辅助的 dmpz 配体最终封闭了环。电喷雾质谱表明 SD/Co8a 和 SD/Co8b 在 CHCl 中高度稳定。磁性分析表明 SD/Co8a 宣布 Co(II)离子之间存在反铁磁相互作用。此外，在温和条件下，它们在频哪醇硼烷存在下都对酮的硼氢化反应表现出良好的均相催化活性。