RT Journal Article
T1 Heavyweight Champion: Caesium Diorganophosphides Outperform Lighter Congeners in the Catalytic Hydrophosphination of Alkenes and Alkynes
A1 Krämer, F.
A1 Crabbe, Michelle H.
A1 Fernández López, Israel
A1 Mulvey, Robert E.
AB We present a study of the ability of our recently reported well-defined crown ether-coordinated alkali metal phosphides 1AM to catalyze hydrophosphination (HP) of alkynes and alkenes. In a comparative study including reaction monitoring by 1H NMR spectroscopy, we show that the activity of caesium compound 1Cs greatly exceeds that of its lighter congeners, enabling us to solve some reported challenges of catalytic hydrophosphination. Through the rarely used application of dialkyl phosphines, we were able to produce trialkyl phosphines from HP of styrene derivatives and activated as well as non-activated alkynes by catalytic HP with nBu2PH and tBu2PH. Using tBuPhPH, P-chiral products were obtained, still in racemic mixtures showcasing this system's potential. We also proved the method is suited for preparing unsymmetrical ethylene-bridged bisphosphines by HP of Ph2P(vinyl) isolable in high yields. These advances hint that well-defined organocaesium compounds could make a long-term impact in chemistry.
PB Wiley
YR 2025
FD 2025-09-10
LK https://hdl.handle.net/20.500.14352/131560
UL https://hdl.handle.net/20.500.14352/131560
LA eng
NO Krämer, Felix, et al. «Heavyweight Champion: Caesium Diorganophosphides Outperform Lighter Congeners in the Catalytic Hydrophosphination of Alkenes and Alkynes». Angewandte Chemie International Edition, vol. 64, n.o 44, octubre de 2025, p. e202516376. DOI.org (Crossref), https://doi.org/10.1002/anie.202516376.
NO Ministerio de Ciencia, Innovación y Universidades
NO Agencia Estatal de Investigación (España)
DS Docta Complutense
RD 26 mar 2026