Triplet Metallovinylidenes of Palladium and Platinum Based on a Chelating P/Diazoalkene Ligand
Triplet carbenes featuring a metal adjacent to the carbene center (metallocarbenes; R─C─M) are an emerging class of diradicals within the field of reactive intermediates. Here, we report the synthesis of the first spectroscopically characterized triplet metallovinylidenes (R─C→M; M = Pt, Pd). The synthetic access is based on a rigid P/C chelating diazoalkene ligand and its coordination to Pt and Pd. The C/P chelating ligand geometrically constrains the R─C→M angle and inhibits free bending. Irradiation of the free diazoalkene ligand generates a triplet vinylidene, characterized by Q-band electron paramagnetic resonance (EPR) spectroscopy. Irradiation of the metal coordination complexes (Pt and Pd) affords triplet metallovinylidenes, which were characterized at low temperatures including photochemically triggered in crystallo X-ray diffraction. Combined FD-FT THz-EPR spectroscopy and SQUID measurements allowed the determination of the large triplet zero-field splitting (ZFS) with D values of 124.5 cm<sup>-1</sup> (Pt) and 8.0 cm<sup>-1</sup> (Pd) in excellent agreement with the electronic structure obtained by high-level quantum chemical calculations.
Authors
- Dimitrios A. Pantazis (ORCID: https://orcid.org/0000-0002-2146-9065)
- Μαρία Δρόσου (ORCID: https://orcid.org/0000-0002-4550-710X)
- Tarek Al Said (ORCID: https://orcid.org/0000-0002-9057-5451)
- Joris van Slageren (ORCID: https://orcid.org/0000-0002-0855-8960)
- Müge Kasanmascheff (ORCID: https://orcid.org/0000-0002-8964-8924)
- Alexander Allgaier (ORCID: https://orcid.org/0009-0006-0689-6858)
- Max Martin Hansmann (ORCID: https://orcid.org/0000-0003-3107-1445)
- Yury Kutin (ORCID: https://orcid.org/0000-0001-9613-0771)
- Patrick W. Antoni
- Julian J. Holstein (ORCID: https://orcid.org/0000-0002-8385-7805)
- Alexander Schnegg (ORCID: https://orcid.org/0000-0002-2362-0638)
- Max Amann
Institutions
- University of Stuttgart (DE)
- TU Dortmund University (DE)
- Helmholtz-Zentrum Berlin für Materialien und Energie (DE)
- Technische Universität Darmstadt (DE)
- Max-Planck-Institut für Kohlenforschung (DE)
- Max Planck Institute for Chemical Energy Conversion (DE)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-11-10
- DOI
- https://doi.org/10.1002/anie.202516032
- Citations
- 2
- Primary Topic
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Alexander von Humboldt-Stiftung
- Deutsche Forschungsgemeinschaft
- Max-Planck-Gesellschaft
- Helmholtz-Zentrum Berlin für Materialien und Energie
- Deutsches Elektronen-Synchrotron