A Four‐Coordinate Pr 4+ Imidophosphorane Complex

Boggiano, Andrew C.; Chowdhury, Sabyasachi Roy; Roy, Michael D.; Bernbeck, Maximilian G.; Greer, Samuel M.; Vlaisavljevich, Bess; La Pierre, Henry S.

doi:10.1002/anie.202409789

Title: A Four‐Coordinate Pr ⁴⁺ Imidophosphorane Complex

Journal Article · 17 September 2024 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202409789 · OSTI ID:2446723

Boggiano, Andrew C. ^[1]; Chowdhury, Sabyasachi Roy ^[2]; Roy, Michael D. ^[1]; Bernbeck, Maximilian G. ^[1]; Greer, Samuel M. ^[3]; Vlaisavljevich, Bess ^[2];

^[4]

School of Chemistry &, Biochemistry Georgia Institute of Technology Atlanta GA 30332-0400 USA
Department of Chemistry University of South Dakota Vermillion SD 57069 USA
Chemistry Division Los Alamos National Laboratory Los Alamos NM 87545 USA
School of Chemistry &, Biochemistry Georgia Institute of Technology Atlanta GA 30332-0400 USA, Nuclear and Radiological Engineering and Medical Physics Program School of Mechanical Engineering Georgia Institute of Technology Atlanta GA 30332-0400 USA

Abstract The imidophosphorane ligand, [NP ^t Bu ₃ ] ⁻ ( ^t Bu= tert ‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr ⁴⁺ (NP ^t Bu ₃ ) ₄ ] ( 1‐Pr ), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L ₃ ‐edge X‐ray near‐edge spectroscopies. Variable‐temperature direct‐current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce ³⁺ analogue, driven by increased crystal field. The four‐coordinate environment around Pr ⁴⁺ in 1‐Pr , which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin‐orbit coupling in a molecular tetravalent lanthanide within a pseudo‐tetrahedral coordination geometry.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515; SC0023022

OSTI ID:: 2446723

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition); ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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