Transient Triplet Metallopnictinidenes M–Pn (M = Pd<sup>II</sup>, Pt<sup>II</sup>; Pn = P, As, Sb): Characterization and Dimerization
Nitrenes (R-N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R-Pn; Pn = P-Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M-Pn═Pn-M} (M = Pd<sup>II</sup>, Pt<sup>II</sup>; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M-Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M-P} dominated by heavy pnictogen atom induced spin-orbit coupling.
Authors
- Tarek Al Said (ORCID: https://orcid.org/0000-0002-9057-5451)
- Marc C. Neben (ORCID: https://orcid.org/0009-0007-9620-2457)
- Richard R. Thompson (ORCID: https://orcid.org/0000-0002-2181-9846)
- Gerard P. Van Trieste (ORCID: https://orcid.org/0000-0002-4270-5880)
- Kevin Dollberg (ORCID: https://orcid.org/0000-0001-5191-6383)
- Igor Tkach (ORCID: https://orcid.org/0000-0002-5417-7536)
- Sven Schneider (ORCID: https://orcid.org/0000-0002-8432-7830)
- Max C. Holthausen (ORCID: https://orcid.org/0000-0001-7283-8329)
- Alexander Schnegg (ORCID: https://orcid.org/0000-0002-2362-0638)
- David C. Powers (ORCID: https://orcid.org/0000-0003-3717-2001)
- Hendrik Verplancke (ORCID: https://orcid.org/0000-0002-3587-845X)
- Carsten von Hänisch
- Serhiy Demeshko
- Nils Wegerich
Institutions
- Goethe University Frankfurt (DE)
- University of Idaho (US)
- Philipps University of Marburg (DE)
- Helmholtz-Zentrum Berlin für Materialien und Energie (DE)
- Mitchell Institute (US)
- Max Planck Institute for Chemical Energy Conversion (DE)
- University of Göttingen (DE)
- Texas A&M University (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-01-29
- DOI
- https://doi.org/10.1021/jacs.4c16830
- Citations
- 19
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 10.21
Funders
- Welch Foundation
- Alexander von Humboldt-Stiftung
- Deutsche Forschungsgemeinschaft
- Basic Energy Sciences