Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes

Catalysts

Alexander M. Kirillov¹  Marina V. Kirillova¹  Jinzhong Gu²  Chumin Liang³  Xunzhong Zou³  Yu Li³ 

[1] Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal;College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China;Guangdong Research Center for Special Building Materials and Its Green Preparation Technology/Foshan Research Center for Special Functional Building Materials and Its Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China;

关键词: hydrothermal synthesis;    coordination polymers;    crystal structures;    metal–organic frameworks;    carboxylate ligands;    heterogeneous catalysis;   

DOI  :  10.3390/catal11020204

来源: DOAJ

【 摘 要 】

Three 2D coordination polymers, [Cu₂(µ₄-dpa)(bipy)₂(H₂O)]_n∙6nH₂O (1), [Mn₂₍µ₆-dpa)(bipy)₂]_n (2), and [Zn₂(µ₄-dpa)(bipy)₂(H₂O)₂]_n·2nH₂O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H₄dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal–organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

【 授权许可】

Unknown