Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex
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(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. 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.
- Authors:
-
[2];
[3];
[4];
[1];
[1];
[4];
[2];
[1]
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Univ. of Buffalo, NY (United States)
- Univ. of Pennsylvania, Philadelphia, PA (United States); Eramet Ideas, Trappes (France)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- OSTI Identifier:
- 1970694
- Grant/Contract Number:
- SC0020169; AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 145; Journal Issue: 2; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Actinides; Electronic structure; Isolation; Ligands; Nitrides
Citation Formats
Wilson, Henry H., Yu, Xiaojuan, Cheisson, Thibault, Smith, Patrick W., Pandey, Pragati, Carroll, Patrick J., Minasian, Stefan G., Autschbach, Jochen, and Schelter, Eric J. Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex. United States: N. p., 2023.
Web. doi:10.1021/jacs.2c12145.
Wilson, Henry H., Yu, Xiaojuan, Cheisson, Thibault, Smith, Patrick W., Pandey, Pragati, Carroll, Patrick J., Minasian, Stefan G., Autschbach, Jochen, & Schelter, Eric J. Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex. United States. https://doi.org/10.1021/jacs.2c12145
Wilson, Henry H., Yu, Xiaojuan, Cheisson, Thibault, Smith, Patrick W., Pandey, Pragati, Carroll, Patrick J., Minasian, Stefan G., Autschbach, Jochen, and Schelter, Eric J. Thu .
"Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex". United States. https://doi.org/10.1021/jacs.2c12145. https://www.osti.gov/servlets/purl/1970694.
@article{osti_1970694,
title = {Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex},
author = {Wilson, Henry H. and Yu, Xiaojuan and Cheisson, Thibault and Smith, Patrick W. and Pandey, Pragati and Carroll, Patrick J. and Minasian, Stefan G. and Autschbach, Jochen and Schelter, Eric J.},
abstractNote = {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. 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.},
doi = {10.1021/jacs.2c12145},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 145,
place = {United States},
year = {Thu Jan 05 00:00:00 EST 2023},
month = {Thu Jan 05 00:00:00 EST 2023}
}
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