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Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-05 , DOI: 10.1021/jacs.2c12145 Henry H Wilson 1 , Xiaojuan Yu 2 , Thibault Cheisson 1 , Patrick W Smith 3 , Pragati Pandey 1 , Patrick J Carroll 1 , Stefan G Minasian 3 , Jochen Autschbach 2 , Eric J Schelter 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-05 , DOI: 10.1021/jacs.2c12145 Henry H Wilson 1 , Xiaojuan Yu 2 , Thibault Cheisson 1 , Patrick W Smith 3 , Pragati Pandey 1 , Patrick J Carroll 1 , Stefan G Minasian 3 , Jochen Autschbach 2 , Eric J Schelter 1
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Complexes featuring lanthanide–ligand multiple bonds are rare and highly reactive. They are important synthetic targets to understand 4f/5d-bonding in comparison to d-block and actinide congeners. Herein, the isolation and characterization of a bridging cerium(IV)-nitride complex: [(TriNOx)Ce(Li2μ-N)Ce(TriNOx)][BArF4] is reported, the first example of a molecular cerium-nitride. The compound was isolated by deprotonating a monometallic cerium(IV)-ammonia complex: [CeIV(NH3)(TriNOx)][BArF4]. The average Ce═N bond length of [(TriNOx)Ce(Li2μ-N)Ce(TriNOx)][BArF4] was 2.117(3) Å. Vibrational studies of the 15N-isotopomer exhibited a shift of the Ce═N═Ce asymmetric stretch from ν = 644 cm–1 to 640 cm–1, and X-ray spectroscopic studies confirm the +4 oxidation state of cerium. Computational analyses showed strong involvement of the cerium 4f shell in bonding with overall 16% and 11% cerium weight in the σ- and π-bonds of the Ce═N═Ce fragment, respectively.
中文翻译：
桥接铈 (IV) 氮化物的合成与表征
以镧系元素-配体多重键为特征的配合物很少见且具有高反应性。与 d 区和锕系元素同系物相比，它们是了解 4f/5d 键合的重要合成目标。在此，报告了桥接铈 (IV)-氮化物络合物的分离和表征：[(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ]，分子铈-氮化物。通过使单金属铈 (IV)-氨络合物：[Ce IV (NH 3 )(TriNOx)][BAr F 4 ] 去质子化来分离该化合物。[(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ]的平均Ce=N键长为2.117(3) Å。15的振动研究N-同位素异构体表现出 Ce=N=Ce 不对称拉伸从 ν = 644 cm –1到 640 cm –1的偏移，并且 X 射线光谱研究证实了铈的 +4 氧化态。计算分析表明，铈 4f 壳强烈参与结合，在 Ce=N=Ce 片段的 σ- 和 π- 键中分别有 16% 和 11% 的铈重量。
更新日期：2023-01-05
中文翻译：
桥接铈 (IV) 氮化物的合成与表征
以镧系元素-配体多重键为特征的配合物很少见且具有高反应性。与 d 区和锕系元素同系物相比，它们是了解 4f/5d 键合的重要合成目标。在此，报告了桥接铈 (IV)-氮化物络合物的分离和表征：[(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ]，分子铈-氮化物。通过使单金属铈 (IV)-氨络合物：[Ce IV (NH 3 )(TriNOx)][BAr F 4 ] 去质子化来分离该化合物。[(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ]的平均Ce=N键长为2.117(3) Å。15的振动研究N-同位素异构体表现出 Ce=N=Ce 不对称拉伸从 ν = 644 cm –1到 640 cm –1的偏移，并且 X 射线光谱研究证实了铈的 +4 氧化态。计算分析表明，铈 4f 壳强烈参与结合，在 Ce=N=Ce 片段的 σ- 和 π- 键中分别有 16% 和 11% 的铈重量。
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