Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study
Molecular transition metal phosphides (TMPs) containing a Rh<sub>2</sub>P<sub>2</sub> and unprecedented Rh<sub>4</sub>P<sub>4</sub> core could be generated from Na[OCP] and rhodium(I) precursor complexes carrying the bischelating tropPPh<sub>2</sub> ligand. These reaction proceed through a formal P-transfer step (trop = 5<i>H</i>-dibenzo[<i>a</i>,<i>d</i>]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(I) center. With the related tetradentate ligand trop<sub>3</sub>P and tridentate ligand trop<sub>2</sub>PPh the first neutral and anionic [Rh<sub><i>x</i></sub>(L)<sub><i>n</i></sub>(PCO)<sub><i>y</i></sub>]<sub><i>z</i></sub> complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(I) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.
Authors
- Peter Coburger (ORCID: https://orcid.org/0000-0003-1387-4148)
- Zhongshu Li (ORCID: https://orcid.org/0000-0002-5425-2524)
- Hansjörg Grützmacher
Institutions
- University of Arizona (US)
- Sun Yat-sen University (CN)
- ETH Zurich (CH)
- Technical University of Munich (DE)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt02274f
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Science Foundation
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- Eidgenössische Technische Hochschule Zürich