Fig. 2: Synthesis of uranium–dinitrogen complexes 1–5. | Nature Chemistry

Fig. 2: Synthesis of uranium–dinitrogen complexes 1–5.

From: Catalytic and stoichiometric stepwise conversion of side-on bound dinitrogen to ammonia mediated by a uranium complex

Fig. 2: Synthesis of uranium–dinitrogen complexes 1–5.

Synthesis of the previously reported pernitride-bridged complex [{UIV(TrenDMBS)}2(μ-η2:η2-N2)], 1, from [UIVTrenDMBS)Cl] via a modified procedure, followed by reduction of 1 to yield the N23− radical-bridged complexes [K(2.2.2-cryptand)][{UIV(TrenDMBS)}2(μ-η2:η2-N2)] (2-crypt), [Li{UIV(TrenDMBS)}2(μ-η2:η2-N2)] (2-Li) and [K{UIV(TrenDMBS)}2(μ-η2:η2-N2)] (2-K). Further reduction yields the hydrazido(4–)-bridged complex [Li2{UIV(TrenDMBS)}2(μ-η2:η2-N2)] (3) and ultimately leads to splitting of the N2 molecule, affording the bis-nitride complex [Li4(OEt2){UIV(TrenDMBS)}2(μ-N)2] (4). Cleavage of the hydrazido moiety is observed upon reaction of 3 with dihydrogen, and allows the isolation of the nitrido/imido-bridged complex [Li3{UIV(TrenDMBS)}2(μ-N)(μ-NH)] (5).

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