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

Abstract

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 σ bonding and, specifically, the higher participation of 4f electrons accounts for the stronger σ covalent interactions in 2-Ce(PN*) as compared to 2-Tb(PN*).

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Article information


Submitted
08 Mar 2020
Accepted
16 May 2020
First published
18 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Accepted Manuscript
Article type
Edge Article

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

N. T. Rice, I. A. Popov, D. R. Russo, T. P. Gompa, A. Ramanathan, J. Bacsa, E. R. Batista, P. Yang and H. S. La Pierre, Chem. Sci., 2020, Accepted Manuscript , DOI: 10.1039/D0SC01414A

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