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A New Cobalt(III)/[Mo6O19]2− Heterogeneous Catalyst for Promoting the Oxidative Coupling of Amines to Imines

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Abstract

Currently, the efficient preparation of imines is still a great challenge under mild conditions. In this article, by incorporating 2-acetylpyridine thiosemicarbazone (HL), Co(NO3)2·6H2O and Na2MoO4·2H2O, a new compound [Co(L)2]2[Mo6O19] (1) was prepared and characterized by elemental analysis (EA), infrared (IR) spectra, ultraviolet–visible (UV–Vis) spectra, powder X-ray diffractometry (PXRD) spectra, X-ray photoelectron spectroscopy (XPS) and X-ray single-crystal diffraction. 1 could be used as a heterogeneous catalyst for oxidative coupling of amines in a comparatively mild condition. Furthermore, 1 exhibited remarkable catalytic performance for oxidation coupling of amines to imines with high yield in the presence of tert-butyl hydroperoxide (TBHP) (up to 92%). Kinetic measurements of the oxidation of benzylamine suggest that the rate law is r = k′[BnNH2][TBHP] (k′ = k[cat] = 0.2338 L mol−1 h−1). Additionally, 1 can be recycled at least three times without a distinct loss of activity.

Graphic Abstract

A new compound [Co(L)2]2[Mo6O19] (1) (HL = 2-acetylpyridine thiosemicarbazone) has been synthesized and characterized. Furthermore, 1 can efficiently catalyze the oxidative coupling of amines to imines with high activity and exhibited good recyclability and high stability.

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Acknowledgements

We thank the National Natural Science Foundation of China (21671055, 21601048), the Natural Science Foundation Project of Henan province (162300410012), and Open Research Fund of Henan Key Laboratory of Polyoxometalate Chemistry (HNPOMKF1601).

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Correspondence to Qiuxia Han or Mingxue Li.

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Zhao, M., Li, J., Xing, C. et al. A New Cobalt(III)/[Mo6O19]2− Heterogeneous Catalyst for Promoting the Oxidative Coupling of Amines to Imines. Catal Lett 150, 753–761 (2020). https://doi.org/10.1007/s10562-019-02965-7

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Keywords

  • Isopolyoxometalate
  • Heterogeneous catalyst
  • Oxidation
  • Imines