Coordination-Induced N-H Bond Splitting of Ammonia and Primary Amine of CuI -MOFs.

We report a porous three-dimensional anionic tetrazolium based CuI -MOF 1, which is capable of cleaving the N-H bond of ammonia and primary amine, as well as the O-H bond of H2 O along with spontaneous H2 evolution. In the gas-solid phase reaction of 1 with ammonia and water vapor, CuI -MOF 1 was gradually oxidized to NH2 -CuII -MOF and OH-CuII -MOF, through single-crystal-to-single-crystal (SCSC) structural transformations, which was confirmed by XPS, PXRD and X-ray single-crystal diffraction. Density functional theory (DFT) demonstrated that CuI -MOF could lower N-H bond dissociation free energy of ammonia through coordination-induced bond weakening and promote H2 evolution by the reduction potential of 1. To our knowledge, this is the first example of MOFs that activate ammonia and amine in gas-solid manner. © 2021 Wiley-VCH GmbH.

Citation

Kuan Gao, Chao Huang, Yan Qiao, Shasha Wang, Jie Wu, Hongwei Hou. Coordination-Induced N-H Bond Splitting of Ammonia and Primary Amine of CuI -MOFs. Chemistry (Weinheim an der Bergstrasse, Germany). 2021 Jul 02;27(37):9499-9502

PMID: 33998739

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