Solvent‐Dependent C(sp<sup>3</sup>)−CF<sub>3</sub> Reductive Elimination from Neutral Four‐Coordinate Cu(III) Complexes
A solvent dependent C(sp<sup>3</sup>)-CF<sub>3</sub> bond-forming reductive elimination from neutral four-coordinate Cu(III) complexes [(L)Cu<sup>III</sup>(CF<sub>3</sub>)<sub>2</sub>(CH<sub>2</sub>CO<sub>2</sub> <sup>t</sup>Bu)] (L=pyridine or its derivatives) is described. Reactions in less polar solvent ClCH<sub>2</sub>CH<sub>2</sub>Cl proceed via a concerted bond breaking/bond forming process along with the reorientation of the ligand, while reaction in polar solvent DMF occurs via a rate limiting ligand-dissociation, followed by C(sp<sup>3</sup>)-CF<sub>3</sub> reductive elimination from the resulting three-coordinate intermediate. These mechanistic proposals are supported by kinetic studies that included ligand and temperature effects, as well as DFT calculations.
Authors
- Yuecheng Weng
- Xuebing Leng (ORCID: https://orcid.org/0000-0003-3291-8695)
- Xiao‐Song Xue (ORCID: https://orcid.org/0000-0003-4541-8702)
- Deng Pan (ORCID: https://orcid.org/0000-0002-9007-0744)
- Jian Wu (ORCID: https://orcid.org/0009-0008-6405-3685)
Institutions
- Shanghai Institute of Organic Chemistry (CN)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-01-09
- DOI
- https://doi.org/10.1002/chem.202403620
- Citations
- 3
- Primary Topic
- Asymmetric Hydrogenation and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 1.61