C–P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands
The reactivity of ruthenium hydride complexes supported by 2-((di-<i>tert</i>-butylphosphaneyl)methyl)pyridine, <b>L1</b> and 2-(di-<i>tert</i>-butylphosphaneyl)pyridine, <b>L2</b>, was explored. The reaction of {Ru(COD)Cl<sub>2</sub>}<sub><i>x</i></sub> with <b>L1</b> in the presence of base and 10 bar of H<sub>2</sub> gave the expected complex [Ru(L1)<sub>2</sub>(H)Cl], <b>1</b>, while the same reaction with <b>L2</b> gave [Ru(L2)(P(H)<sup><i>t</i></sup>Bu<sub>2</sub>)(H)Cl], <b>2</b>, that results from the cleavage of a C-P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)<sub>2</sub>(H)Cl], <b>3</b>, and that this species decomposes to give complex <b>2</b> and is in equilibrium with [Ru(L<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>], <b>4</b>. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex <b>2</b> is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).
Authors
- Cláudia A. Figueira (ORCID: https://orcid.org/0000-0002-9826-4332)
- Ana M. Martins (ORCID: https://orcid.org/0000-0002-3922-5501)
- Luı́s F. Veiros (ORCID: https://orcid.org/0000-0001-5841-3519)
- M.J. Ferreira (ORCID: https://orcid.org/0000-0002-7909-637X)
- Clara S. B. Gomes (ORCID: https://orcid.org/0000-0003-3672-0045)
- Vanessa R. G. Cacho
- Mariana Sardo (ORCID: https://orcid.org/0000-0003-3208-4387)
Institutions
- University of Lisbon (PT)
- Rede de Química e Tecnologia (PT)
- University of Aveiro (PT)
- Universidade Nova de Lisboa (PT)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-11-26
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c04275
- Citations
- 1
- Primary Topic
- Asymmetric Hydrogenation and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.16
Funders
- Fundação para a Ciência e a Tecnologia