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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.
Affiliation
  • Wilson HH; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Yu X; Department of Chemistry, University of Buffalo, 732 Natural Sciences Complex, Buffalo, New York 14260, United States.
  • Cheisson T; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Smith PW; Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
  • Pandey P; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Carroll PJ; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Minasian SG; Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
  • Autschbach J; Department of Chemistry, University of Buffalo, 732 Natural Sciences Complex, Buffalo, New York 14260, United States.
  • Schelter EJ; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
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 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.
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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
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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