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

Natalie T. Rice; Ivan A. Popov; Rebecca K. Carlson; Samuel M. Greer; Andrew C. Boggiano; Benjamin W. Stein; John Bacsa; Enrique R. Batista; Ping Yang; Henry S. La Pierre

doi:10.1039/D2DT00758D

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

Natalie T. Rice,

‡^a Ivan A. Popov,‡^bc Rebecca K. Carlson,^b Samuel M. Greer,^d Andrew C. Boggiano,

^a Benjamin W. Stein,

^d John Bacsa,^a Enrique R. Batista,

*^b Ping Yang

*^b and Henry S. La Pierre

*^ae

Author affiliations

* Corresponding authors

^a School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA
E-mail: hsl@gatech.edu

^b Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
E-mail: erb@lanl.gov, pyang@lanl.gov

^c Department of Chemistry, The University of Akron, Akron, OH 44325-3601, USA

^d Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA

^e Nuclear and Radiological Engineering and Medical Physics Program, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA

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.

Dalton Transactions

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

Abstract

Supplementary files

Article information

Download Citation

Author version available

Permissions

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

Social activity

Search articles by author

Spotlight

Advertisements

Dalton Transactions