Reaction of [K(DME)][Th{N(R)(SiMe₂CH₂)}₂(NR₂)] (R = SiMe₃) with 1 equiv. of [U(NR₂)₃(NH₂)] (1) in THF, in the presence of 18-crown-6, results in formation of a bridged uranium–thorium nitride complex, [K(18-crown-6)(THF)₂][(NR₂)₃U^IV(μ-N)Th^IV(NR₂)₃] (2), which can be isolated in 48% yield after work-up. Complex 2 is the first isolable molecular mixed-actinide nitride complex. Also formed in the reaction is the methylene-bridged mixed-actinide nitride, [K(18-crown-6)][K(18-crown-6)(Et₂O)₂][(NR₂)₂U(μ-N)(μ–κ²-C,N–CH₂SiMe₂NR)Th(NR₂)₂]₂ (3), which can be isolated in 34% yield after work-up. Complex 3 is likely generated by deprotonation of a methyl group in 2 by [NR₂]⁻, yielding the new μ-CH₂ moiety and HNR₂. Reaction of 2 with 0.5 equiv. of I₂ results in formation of a U^V/Th^IV bridged nitride, [(NR₂)₃U^V(μ-N)Th^IV(NR₂)₃] (4), which can be isolated in 42% yield after work-up. The electronic structure of 4 was analyzed with EPR spectroscopy, SQUID magnetometry, and NIR-visible spectroscopy. This analysis demonstrated that the energies of 5f orbitals of 4 are largely determined by the strong ligand field exerted by the nitride ligand.

中文翻译：

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异质双金属锕系氮化物的合成及其键合分析

[K(DME)][Th{ N (R)(SiMe ₂ C H ₂ )} ₂ (NR ₂ )] (R = SiMe ₃ ) 与 1 equiv 的反应。[U(NR ₂ ) ₃ (NH ₂ )] ( 1 ) 在 THF 中，在 18-crown-6 存在下，导致形成桥接铀-氮化钍复合物，[K(18-crown-6) (THF) ₂ ][(NR ₂ ) ₃ U ^IV (μ-N)Th ^IV (NR ₂ ) ₃ ] ( 2 )，后处理后可以以 48% 的收率分离。复合体2是第一个可分离的分子混合锕系氮化物配合物。在反应中还形成亚甲基桥连的混合锕系氮化物，[K(18-crown-6)][K(18-crown-6)(Et ₂ O) ₂ ][(NR ₂ ) ₂ U(μ -N)(μ–κ ² - C , N –CH ₂ SiMe ₂ NR)Th(NR ₂ ) ₂ ] ₂ ( 3 )，后处理后可以以 34% 的收率分离。复合物3很可能是通过 [NR ₂ ] ^-对2中的甲基进行去质子化生成的，从而产生新的 μ-CH ₂部分和 HNR ₂。2与 0.5 equiv 的反应。的 I ₂导致形成 U ^V /Th ^IV桥接氮化物，[(NR ₂ ) ₃ U ^V (μ-N)Th ^IV (NR ₂ ) ₃ ] ( 4 )，其分离后产率为 42%工作。用 EPR 光谱、SQUID 磁强计和 NIR-可见光谱分析了4的电子结构。该分析表明，4的 5f 轨道的能量很大程度上取决于氮化物配体施加的强配体场。