AI Article Synopsis
- Kinetic, spectroscopic, and computational studies show that mono-oxidation of the bis-phosphine ligand is crucial for forming the active catalyst in Pd-catalyzed C-H arylation reactions.
- The bis-phosphine mono-oxide acts as a hemilabile, bidentate ligand that can successfully participate in catalytic processes, achieving reaction rates similar to the original Pd(II)/xantphos system.
- The role of carboxylate bases is highlighted for both activating the catalyst and facilitating the reaction, while excess phosphine ligand hinders the process.
Article Abstract
Kinetic, spectroscopic, crystallographic, and computational studies probing a Pd-catalyzed C-H arylation reaction reveal that mono-oxidation of the bis-phosphine ligand is critical for the formation of the active catalyst. The bis-phosphine mono-oxide is shown to be a hemilabile, bidentate ligand for palladium. Isolation of the oxidative addition adduct, with structural elucidation by X-ray analysis, showed that the mono-oxide was catalytically competent, giving the same reaction rate in the productive reaction as the Pd(II)/xantphos precursor. A dual role for the carboxylate base in both catalyst activation and reaction turnover was demonstrated, along with the inhibiting effect of excess phosphine ligand. The generality of the role of phosphine mono-oxide complexes in Pd-catalyzed coupling processes is discussed.
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| http://dx.doi.org/10.1021/jacs.5b01913 | DOI Listing |
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