Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex.
J Am Chem Soc
; 145(2): 781-786, 2023 01 18.
Article
in En
| MEDLINE
| ID: mdl-36603174
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 CeâN 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 CeâNâCe 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 CeâNâCe fragment, respectively.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Cerium
/
Lanthanoid Series Elements
Language:
En
Journal:
J Am Chem Soc
Year:
2023
Document type:
Article
Affiliation country:
United States