Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex

Wilson, Henry H.; Yu, Xiaojuan; Cheisson, Thibault; Smith, Patrick W.; Pandey, Pragati; Carroll, Patrick J.; Minasian, Stefan G.; Autschbach, Jochen; Schelter, Eric J.

doi:10.1021/jacs.2c12145

DOE OSTI · 1970694

Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex

Wilson, Henry H.·Yu, Xiaojuan·Cheisson, Thibault·Smith, Patrick W.·Pandey, Pragati·Carroll, Patrick J.·Minasian, Stefan G.·Autschbach, Jochen·Schelter, Eric J.

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Abstract

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(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ] is reported, the first example of a molecular cerium-nitride. The compound was isolated by deprotonating a monometallic cerium(IV)-ammonia complex: [Ce IV (NH 3 )(TriNOx)][BAr F 4 ]. The average Ce=N bond length of [(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ] was 2.117(3) Å. Vibrational studies of the 15 N-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. Furthermore, 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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Actinides Electronic structure Isolation Ligands Nitrides

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Wilson, Henry H., Yu, Xiaojuan, Cheisson, Thibault, Smith, Patrick W., Pandey, Pragati, Carroll, Patrick J., Minasian, Stefan G., Autschbach, Jochen, Schelter, Eric J.. 2023-01-05. Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex. https://doi.org/10.1021/jacs.2c12145

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