Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.
Voloshkin, Vladislav A
Cazin, Catherine S. J.
Nolan, Steven P.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Embargo End Date2022-04-28
Permanent link to this recordhttp://hdl.handle.net/10754/669033
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AbstractWe report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1-2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(i) dimer formation undesirable in catalysis.
CitationLiu, Y., Voloshkin, V. A., Scattolin, T., Cavallo, L., Dereli, B., Cazin, C. S. J., & Nolan, S. P. (2021). Conversion of Pd(i) off-cycle species into highly efficient cross-coupling catalysts. Dalton Transactions, 50(16), 5420–5427. doi:10.1039/d1dt00929j
SponsorsWe gratefully acknowledge VLAIO (SBO project CO2PERATE) and the Special Research Fund (BOF) of Ghent University. Funding of the iBOF project C3 (BOF20/IBF/010) is also gratefully acknowledge. Umicore AG is gratefully acknowledged for generous gifts of materials. Y. L. thanks the CSC for a PhD fellowship.
PublisherRoyal Society of Chemistry (RSC)
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