Co@CoO-catalyzed reductive amination driven by hydride-like NH2δ‒ species

doi:10.1016/S1872-2067(22)64196-2

Abstract

Abstract:

Owing to the wide application of primary amines, their selective production via reductive amination has become a crucial research topic. Various metal-supported catalysts (Pt, Ru, Rh, Ir, Co, Ni, etc.) have been investigated, and metallic species have been recognized as active sites in recent years. Herein, we reveal for the first time that CoO species containing oxygen vacancies within a core-shell-structured Co@CoO catalyst accelerate the ammonolysis of Schiff bases, key intermediates in reductive amination, through NH₃ dissociation to hydride-like NH₂^δ^- species, delivering an excellent reductive amination performance. The catalyst is highly stable and was utilized in 10 catalytic cycles for the amination of biomass-derived cyclopentanone (CPO) to cyclopentylamine (CPA) without deactivation. Various computational models in combination with spectroscopic measurements indicated that this catalyst not only drives the dissociation of H₂ to the active H^δ^- species, but also enables the homolytic cleavage of NH₃ to NH₂^δ^-. D₂ isotopic tracing experiments provided further evidence of the direct involvement of hydride-like NH₂^δ^- species in Schiff base ammonolysis. Theoretical calculations verified the stable co-adsorption of H^δ^- and NH₂^δ^-, which allows the Schiff base to move freely on the surface of the CoO shell and participate extensively in molecular collisions, resulting in exceptional catalytic activity. This is the first study that demonstrates the potential of metal oxide catalysts for the production of primary amines via reductive amination.

Key words: Reductive amination, Hydride-like NH₂^δ^-, Co@CoO, Schiff-base

Wanjun Guo, Zhi-Qiang Wang, Shuang Xiang, Yaxuan Jing, Xiaohui Liu, Yong Guo, Xue-Qing Gong, Yanqin Wang. Co@CoO-catalyzed reductive amination driven by hydride-like NH₂^δ^‒ species[J]. Chinese Journal of Catalysis, 2023, 47: 181-190.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64196-2

https://www.cjcatal.com/EN/Y2023/V47/I4/181

Figures/Tables 6

Fig. 1. Characterization of the Co@CoO catalyst. (a) XRD pattern; (b) HRTEM image; (c) X-band EXAFS spectra in R space; (d) EPR spectrum at -196.15 °C.

Fig. 2. (a) In-situ DRIFT spectrum of Co@CoO under H2/D2 gas atmosphere. (b) NH3-adsorption DRIFT spectrum of Co@CoO. (c,d) Calculated structures for NH3 homolysis and heterolysis on CoO (100): NH3 adsorption, TS of NH3 homolysis ($E_{\text{ads}}^{\hom \text{o}}$(TS)), TS of NH3 heterolysis ($E_{\text{ads}}^{\text{heter}}$(TS)), final state of NH3 homolysis (NH2- + H-), and final state of NH3 heterolysis (NH2- + H+).

Table 1 Catalytic performances of three different CoOx catalysts in reductive amination.

Catalyst	Conversion (%)	Yield (%)
Catalyst	Conversion (%)	1	2	3	4
CoO_x-200	62.7	0	23.6	0	4.1
Co@CoO	99.9	78.5	0	19.5	1.1
CoO_x-300	98.6	45	0	47.1	4.5

Fig. 3. (a) Comparison of the catalytic performances of Co@CoO and other catalysts for reductive amination [9,11,16,17,20,22,23,26,27,53???-57]. Conditions: 2 mmol substrate, 5 mL MeOH, 20 mg Co@CoO, 0.4 MPa NH3, 2 MPa H2, GC yield with 1,4-dioxane as internal standard. a 5 mL 1,4-dioxane as solvent, GC yield using dodecane as an internal standard. (b) Reductive amination of biologically active molecules to the corresponding primary amines. Conditions: 2 mmol substrate, 5 mL MeOH, 20 mg Co@CoO, 100 °C, 0.4 MPa NH3, 2 MPa H2, 5 h, isolated yields of converted hydrochloride salts. (c) Co@CoO stability for the amination of CPO and TEM image of the used catalyst.

Fig. 4. (a) Time curve and possible reaction route for CPO amination. Conditions: 2 mmol CPO, 5 mL MeOH, 20 mg Co@CoO, 0.4 MPa NH3, 2 MPa H2, 70 °C. (b) Schiff base ammonolysis under D2. (c) Calculated Schiff base adsorption structures on reduced CoO (100) surfaces. (Schiff base, H- + Schiff base and NH2-ads + Schiff base).

Fig. 5. Proposed reaction mechanism for imine hydrogenation and Schiff base ammonolysis.

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Co@CoO-catalyzed reductive amination driven by hydride-like NH₂^δ^‒ species

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