Dinitrogen Activation and Conversion by Actinide Complexes

Abstract

The efficient activation and conversion of dinitrogen (N₂) represent a significant challenge in sustainable chemistry, offering potential pathways for synthesizing valuable nitrogen-containing compounds while reducing the environmental impact of traditional nitrogen fixation processes. While transition metal catalysts have been extensively studied for this purpose, actinide complexes have been less explored but have recently emerged as promising candidates due to their unique electronic properties and reactivity. This Perspective systematically examines the recent advances in N₂ activation and conversion mediated by actinide complexes, with a particular focus on their synthesis, mechanistic insights, and catalytic capabilities.

Scheme 1. Synthesis of a Cp*-Supported Mononuclear U(III)–N₂ Complex

Scheme 2. Synthesis of U(V)–N₂ Complex

Scheme 3. Synthesis of N₂-Bridged Fe/U Bimetal Complexes

Scheme 4. Synthetic Route to the First Uranium–N₂ Complex

Scheme 5. Synthesis of the U–N₂–Mo Complex

Scheme 6. Synthesis of Complex 13

Scheme 7. Synthesis of Complex 15

Scheme 8. Synthesis of Complex 16

Scheme 9. Synthesis of N₂^•3–-Bridged Diuranium Complexes

Scheme 10. N₂ Reduction and Functionalization Mediated by 20

Scheme 11. N₂ Reduction and Functionalization Mediated by 24

Scheme 12. Binuclear U and Binuclear Th Complex-Promoted N₂ Activation

Scheme 13. Synthesis of Complex 31

Scheme 14. Synthesis of N₂ Cleavage Product 33

Scheme 15. Cleavage of N₂ though U(III)–P(III) Synergetic Strategy

Figure 1

Computed enthalpy profile (in kcal mol^–1) for the formation of complex 37.

Scheme 16. N₂ Cleavage Mediated by the Cluster with U–Rh Bonds

Scheme 17. N₂ Cleavage by Uranium Azide Complex 43

Scheme 18. Functionalization of N₂ Cleavage Product 44

Figure 2

Computed enthalpy profile (in kcal mol^–1) for the formation of 44 from 25a.

Scheme 19. Synthesis of N₂ Cleavage Product 48

Scheme 20. N₂ Cleavage by the Reduction of 49

Scheme 21. N₂ Cleavage and Functionalization by 25a and 53

Figure 3

Computed enthalpy (in kcal mol^–1) profiles for the formation of 54 and 55.

Scheme 22. Synthesis of the Tetranitride (56) and Hexanitride (57) Clusters