Stepwise Reduction of Dinitrogen by a Uranium-Potassium Complex Yielding a U(VI)/U(IV) Tetranitride Cluster

Multimetallic cooperativity is believed to play a key role in the cleavage of dinitrogen to nitrides (N^3-), but the mechanism remains ambiguous due to the lack of isolated intermediates. Herein, we report the reduction of the complex [K₂{[U^V(OSi(O^tBu)₃)₃]₂(μ-O)(μ-η²:η²-N₂)}], B, with KC₈, yielding the tetranuclear tetranitride cluster [K₆{(OSi(O^tBu)₃)₂U^IV}₃{(OSi(O^tBu)₃)₂U^VI}(μ₄-N)₃(μ₃-N)(μ₃-O)₂], 1, a novel example of N₂ cleavage to nitride by a diuranium complex. The structure of complex 1 is remarkable, as it contains a unique uranium center bound by four nitrides and provides the second example of a trans-N═U^VI═N core analogue of UO₂²⁺. Experimental and computational studies indicate that the formation of the U(IV)/U(VI) tetrauranium cluster occurs via successive one-electron transfers from potassium to the bound N₂^4- ligand in complex B, resulting in N₂ cleavage and the formation of the putative diuranium(V) bis-nitride [K₄{[U^V(OSi(O^tBu)₃)₃]₂(μ-O)(μ-N)₂}], X. Additionally, cooperative potassium binding to the U-bound N₂^4- ligand facilitates dinitrogen cleavage during electron transfer. The nucleophilic nitrides in both complexes are easily functionalized by protons to yield ammonia in 93-97% yield and with excess ¹³CO to yield K¹³CN and KN¹³CO. The structures of two tetranuclear U(IV)/U(V) bis- and mononitride clusters isolated from the reaction with CO demonstrate that the nitride moieties are replaced by oxides without disrupting the tetranuclear structure, but ultimately leading to valence redistribution.