Issue 17, 2022

Spectroscopic and electrochemical characterization of a Pr4+ imidophosphorane complex and the redox chemistry of Nd3+ and Dy3+ complexes

Abstract

The molecular tetravalent oxidation state for praseodymium is observed in solution via oxidation of the anionic trivalent precursor [K][Pr3+(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (1-Pr(NP*)) with AgI at −35 °C. The Pr4+ complex is characterized in solution via cyclic voltammetry, UV-vis-NIR electronic absorption spectroscopy, and EPR spectroscopy. Electrochemical analyses of [K][Ln3+(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (Ln = Nd and Dy) by cyclic voltammetry are reported and, in conjunction with theoretical modeling of electronic structure and oxidation potential, are indicative of principal ligand oxidations in contrast to the metal-centered oxidation observed for 1-Pr(NP*). The identification of a tetravalent praseodymium complex in in situ UV-vis and EPR experiments is further validated by theoretical modeling of the redox chemistry and the UV-vis spectrum. The latter study was performed by extended multistate pair-density functional theory (XMS-PDFT) and implicates a multiconfigurational ground state for the tetravalent praseodymium complex.

Graphical abstract: Spectroscopic and electrochemical characterization of a Pr4+ imidophosphorane complex and the redox chemistry of Nd3+ and Dy3+ complexes

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2022
Accepted
31 Mar 2022
First published
02 Apr 2022

Dalton Trans., 2022,51, 6696-6706

Spectroscopic and electrochemical characterization of a Pr4+ imidophosphorane complex and the redox chemistry of Nd3+ and Dy3+ complexes

N. T. Rice, I. A. Popov, R. K. Carlson, S. M. Greer, A. C. Boggiano, B. W. Stein, J. Bacsa, E. R. Batista, P. Yang and H. S. La Pierre, Dalton Trans., 2022, 51, 6696 DOI: 10.1039/D2DT00758D

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