@article{26d6ab72-dd18-46ab-a865-74b377b383aa,
  abstract     = {{<p>Accessing high-spin configurations of transition metal phosphides defines a dividing line that prevents common properties of solid-state materials from being replicated within multiple-bonded molecular analogs. Here, we report the synthesis of a V<sup>III</sup> phosphaethynolate complex, [(pyrNdipp)<sub>2</sub>V(PCO)] (2) in a halide metathesis with Na(OCP). Exposure of 2 to Lewis-basic ligands induces a one-electron reductive elimination of the PCO<sup>–</sup> moiety, generating V<sup>II</sup> complexes [(pyrNdipp)<sub>2</sub>V(L)<sub>2</sub>] (L = THF, DMAP; 3<sup>THF</sup>, 3<sup>DMAP</sup>). When 2 is instead photolyzed, a cascade of reduction, decarbonylation, and multiple-bond formation steps affords a high-spin and mixed-valent vanadium phosphide, [(pyrNdipp)<sub>2</sub>V═P═V(pyrNdipp)<sub>2</sub>] (4) comprising formal [V<sub>2</sub><sup>III, IV</sup>] nodes. Structural characterization coupled with vibrational, UV–visible, and X-ray spectroscopic studies reveals an S<sub>4</sub> symmetrical [V═P═V] centered architecture conforming to a fully delocalized, mixed-valency description. Theoretical studies demonstrate that 4 evades spin-pairing by leveraging the weak ligand-field splitting at the vanadium nodes, leading to a high-spin, S<sub>T</sub> = 3/2 ground state of this multiple-bonded, weakly Jahn–Teller distorted system.</p>}},
  author       = {{Chandran, Aswin and Sandoval-Pauker, Christian and Pinter, Balazs and Vosch, Tom and Wilhelm, Fabrice and Rogalev, Andrei and Pedersen, Kasper S. and Reinholdt, Anders}},
  issn         = {{0002-7863}},
  language     = {{eng}},
  month        = {{03}},
  number       = {{9}},
  pages        = {{9629--9639}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of the American Chemical Society}},
  title        = {{A Mixed-Valent and High-Spin Vanadium Phosphide}},
  url          = {{http://dx.doi.org/10.1021/jacs.5c20647}},
  doi          = {{10.1021/jacs.5c20647}},
  volume       = {{148}},
  year         = {{2026}},
}