Nitrogen activation and cleavage by a multimetallic uranium complex

Abstract

Multimetallic-multielectron cooperativity plays a key role in the metal-mediated cleavage of N₂ to nitrides (N³⁻). In particular, low-valent uranium complexes coupled with strong alkali metal reducing agents can lead to N₂ cleavage, but often, it is ambiguous how many electrons are transferred from the uranium centers to cleave N₂. Herein, we designed new dinuclear uranium nitride complexes presenting a combination of electronically diverse ancillary ligands to promote the multielectron transformation of N₂. Two heteroleptic diuranium nitride complexes, [K{U^IV(OSi(O^tBu)₃)(N(SiMe₃)₂)₂}₂(μ-N)] (1) and [Cs{U^IV(OSi(O^tBu)₃)₂(N(SiMe₃)₂)}₂(μ-N)] (3-Cs), containing different combinations of OSi(O^tBu)₃ and N(SiMe₃)₂ ancillary ligands, were synthesized. We found that both complexes could be reduced to their U(III)/U(IV) analogues, and the complex, [K₂{U^IV/III(OSi(O^tBu)₃)₂(N(SiMe₃)₂)}₂(μ-N)] (6-K), could be further reduced to a putative U(III)/U(III) species that is capable of promoting the 4e⁻ reduction of N₂, yielding the N₂⁴⁻complex [K₃{U^V(OSi(O^tBu)₃)₂(N(SiMe₃)₂)}₂(μ-N)(μ-η²:η²-N₂)], 7. Parallel N₂ reduction pathways were also identified, leading to the isolation of N₂ cleavage products, [K₃{U^VI(OSi(O^tBu)₃)₂(N(SiMe₃)₂)(N)}(μ-N)₂{U^V(OSi(O^tBu)₃)₂(N(SiMe₃)₂)}]₂, 8, and [K₄{(OSi(O^tBu)₃)₂U^V)(N)}(μ-NH)(μ-κ²:C,N-CH₂SiMe₂NSiMe₃)-{U^V(OSi(O^tBu)₃)₂][K(N(SiMe₃)₂]₂, 9. These complexes provide the first example of N₂ cleavage to nitride by a uranium complex in the absence of reducing alkali metals.