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A Mixed-Valent and High-Spin Vanadium Phosphide

Chandran, Aswin LU ; Sandoval-Pauker, Christian ; Pinter, Balazs ; Vosch, Tom ; Wilhelm, Fabrice ; Rogalev, Andrei ; Pedersen, Kasper S. and Reinholdt, Anders LU (2026) In Journal of the American Chemical Society 148(9). p.9629-9639
Abstract

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 VIII phosphaethynolate complex, [(pyrNdipp)2V(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– moiety, generating VII complexes [(pyrNdipp)2V(L)2] (L = THF, DMAP; 3THF, 3DMAP). When 2 is instead photolyzed, a cascade of reduction, decarbonylation, and multiple-bond formation steps affords a high-spin and mixed-valent... (More)

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 VIII phosphaethynolate complex, [(pyrNdipp)2V(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– moiety, generating VII complexes [(pyrNdipp)2V(L)2] (L = THF, DMAP; 3THF, 3DMAP). 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)2V═P═V(pyrNdipp)2] (4) comprising formal [V2III, IV] nodes. Structural characterization coupled with vibrational, UV–visible, and X-ray spectroscopic studies reveals an S4 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, ST = 3/2 ground state of this multiple-bonded, weakly Jahn–Teller distorted system.

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author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
148
issue
9
pages
11 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:41760593
  • scopus:105032343611
ISSN
0002-7863
DOI
10.1021/jacs.5c20647
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2026 The Authors. Published by American Chemical Society
id
26d6ab72-dd18-46ab-a865-74b377b383aa
date added to LUP
2026-04-27 13:54:12
date last changed
2026-07-08 00:47:05
@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}},
}