Your browser doesn't support javascript.
loading
Spectroscopic and electrochemical characterization of a Pr4+ imidophosphorane complex and the redox chemistry of Nd3+ and Dy3+ complexes.
Rice, Natalie T; Popov, Ivan A; Carlson, Rebecca K; Greer, Samuel M; Boggiano, Andrew C; Stein, Benjamin W; Bacsa, John; Batista, Enrique R; Yang, Ping; La Pierre, Henry S.
Afiliação
  • Rice NT; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA. hsl@gatech.edu.
  • Popov IA; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. erb@lanl.gov.
  • Carlson RK; Department of Chemistry, The University of Akron, Akron, OH 44325-3601, USA.
  • Greer SM; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. erb@lanl.gov.
  • Boggiano AC; Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
  • Stein BW; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA. hsl@gatech.edu.
  • Bacsa J; Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
  • Batista ER; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA. hsl@gatech.edu.
  • Yang P; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. erb@lanl.gov.
  • La Pierre HS; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. erb@lanl.gov.
Dalton Trans ; 51(17): 6696-6706, 2022 May 03.
Article em En | MEDLINE | ID: mdl-35412547
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.
Texto completo
Imprimir
XML
PubMed Links
Buscar no Google

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Dalton Trans Assunto da revista: QUIMICA Ano de publicação: 2022 Tipo de documento: Article País de afiliação: Estados Unidos
Texto completo
Imprimir
XML
PubMed Links
Buscar no Google

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Dalton Trans Assunto da revista: QUIMICA Ano de publicação: 2022 Tipo de documento: Article País de afiliação: Estados Unidos