A Strong‐Acid‐Resistant [Th<sub>6</sub>] Cluster‐Based Framework for Effectively and Size‐Selectively Catalyzing Reductive Amination of Aldehydes with <i>N</i>,<i>N</i>‐Dimethylformamide
Xuerui Tian, Zhiyu Jiang, Sheng‐Li Hou, Han‐Shi Hu, Jun Li, Bin Zhao
Abstract
Abstract Utilization of N,N‐dimethylformamide (DMF) as an amine source and reductant for synthesizing tertiary amines is a promising way to replace the substrates formaldehyde and dimethylamine, and it is desirable to seek porous acid‐resistant catalysts for heterogeneous catalysis of this reaction. Herein, a robust metal–organic framework (MOF) {[Th 6 O 4 (OH) 4 (H 2 O) 6 (BCP) 3 ]⋅10 DMF} n ( 1 ) containing stacked nanocages with a diameter of 1.55 nm was constructed. Compound 1 can maintain its single‐crystal structure even kept in air at 400 °C for 3 h, and in DMF or water at 200 °C for 7 days. Density functional theory (DFT) calculations suggested that the high interaction energy between the [Th 6 O 4 (OH) 4 (H 2 O) 6 ] 12+ clusters and ligands was responsible for the excellent stability of 1 . Catalytic investigations revealed that 1 can effectively and size‐selectively catalyze the reductive amination of aldehydes with DMF, and it can be reused at least five times without obvious loss in catalytic activity.