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Title: Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/d0sc01414a · OSTI ID:1630778
 [1];  [2];  [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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A redox pair of Ce4+ and Ce3+ complexes has been prepared that is stabilized by the [(NP(1,2-bis-tBu-diamidoethane)(NEt2))]1- ligand. Since these complexes are isostructural to the recently reported isovalent terbium analogs, a detailed structural and spectroscopic comparative analysis was pursued via Voronoi–Dirichlet polyhedra analysis, UV-vis-NIR, L3-edge X-ray absorption near edge spectroscopy (XANES), cyclic voltammetry, and natural transitions orbital (NTO) analysis and natural bond orbital (NBO) analysis. The electrochemical studies confirm previous theoretical studies of the redox properties of the related complex [K][Ce3+(NP(pip)3)4] (pip = piperidinyl), 1-Ce(PN). Complex 1-Ce(PN*) presents the most negative Epc of -2.88 V vs. Fc/Fc+ in THF of any cerium complex studied electrochemically. Likewise 1-Tb(PN*) has the most negative Epc for electrochemically interrogated terbium complexes at -1.79 V vs. Fc/Fc+ in THF. Complexes 1-Ce(PN*) and 2-Ce(PN*) were also studied by L3-edge X-ray absorption near edges spectroscopy (XANES) and a comparison to previously reported spectra for 1-Tb(PN*), 2-Tb(PN*), 1-Ce(PN), and, [Ce4+(NP(pip)3)4], 2-Ce(PN), demonstrates similar nf values for all the tetravalent lanthanide complexes. According to the natural bond orbital analysis, a greater covalent character of the M–L bonds is found in 2-Ce(PN*) than in 1-Ce(PN*), in agreement with the shorter Ce–N bonds in the tetravalent counterpart. The greater contribution of Ce orbitals in the Ce–N bonding and, specifically, the higher participation of 4f electrons accounts for the stronger covalent interactions in 2-Ce(PN*) as compared to 2-Tb(PN*).

Research Organization:
Georgia Institute of Technology, Atlanta, GA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
Grant/Contract Number:
SC0019385; AC02-76SF00515; 89233218CNA000001; P41GM103393
OSTI ID:
1630778
Alternate ID(s):
OSTI ID: 1677651; OSTI ID: 1688764
Report Number(s):
LA-UR-20-22218
Journal Information:
Chemical Science, Vol. 11, Issue 24; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

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Linked Research (2)

Figures / Tables (11)

Scheme 1(p. 2)figure Scheme 1
Scheme 2(p. 2)figure Scheme 2
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