N-substituted pyridiniophosphines, processes for their preparation and their use
Prozesse und Methoden (inkl. Screening) : Chemische
Forschungs-Reagenzien : Andere
In coordination chemistry, typical ancillary ligands are anionic or neutral species. Cationic ones are exceptions and, when used, the positively charged groups are normally attached to the periphery and not close to the donating atom. Recently a growing number of studies indicate that cationic ligands depict excellent π-acceptor character that can exceed that of phosphites or polyfluorinated phosphines. This property has been used to increase the Lewis acidity of the metals they coordinate.
A new family of cationic ligands, N-alkyl/aryl pyridiniophosphines, has been synthesized through a short, scalable, and highly modular route.
Evaluation of their electronic properties evidenced weak σ-donor and quite strong π-acceptor character when used as ancillary ligands.
These attributes confer a substantially enhanced π-acidity to the PtII and AuI complexes thereof derived and, as result, they depict an improved ability to activate alkynes towards nucleophilic attack.
This superior performance has been demonstrated along several mechanistically diverse PtII- and AuI catalyzed transformations.
Hendrik Tinnermann, Christian Wille, Manuel Alcarazo: "Synthesis, Structure, and Applications of Pyridiniophosphines", Angew. Chem. Int. Ed. 2014, 53, 8732 –8736
EP priority patent application filed in April 2014.
PCT patent application filed in April 2015, nationalized in EP, US, CA, CN KR, JP, IN.
US9962690, JP6236170B2, EP313742B1 granted.
- Ref.-No.: 0042-4398-LC-WA (445,3 KiB)