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A Four‐Coordinate Pr4+ Imidophosphorane Complex
Journal article   Open access   Peer reviewed

A Four‐Coordinate Pr4+ Imidophosphorane Complex

Andrew C. Boggiano, Sabyasachi Roy Chowdhury, Michael D. Roy, Maximilian G. Bernbeck, Samuel M. Greer, Bess Vlaisavljevich and Henry Storms La Pierre
Angewandte Chemie, Vol.136(43), e202409789
10/21/2024
DOI: 10.1002/ange.202409789
url
https://doi.org/10.1002/ange.202409789View
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Abstract

The imidophosphorane ligand, [NPtBu3]– (tBu = tert‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr4+(NPtBu3)4] (1‐Pr), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L3‐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 Ce3+ analogue, driven by increased crystal field. The four‐coordinate environment around Pr4+ 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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