Phosphorus ligands with a large cavity: synthesis of triethynylphosphines with bulky end caps and application to the rhodium-catalyzed hydrosilylation of ketones.

@article{Ochida2007PhosphorusLW,
  title={Phosphorus ligands with a large cavity: synthesis of triethynylphosphines with bulky end caps and application to the rhodium-catalyzed hydrosilylation of ketones.},
  author={Atsuko Ochida and Masaya Sawamura},
  journal={Chemistry, an Asian journal},
  year={2007},
  volume={2 5},
  pages={609-18}
}
Trialkynylphosphines substituted with bulky triarylsilyl groups at the alkyne termini were synthesized. The new phosphines P(C[triple chemical bond]CSiAr(3))(3) (Ar=3,5-tBu(2)-4-MeOC(6)H(2), 3,5-(Me(3)Si)(2)C(6)H(3)) are uncrowded near the phosphorus atom but bulky in the distal region. As a result, they contain a large cavity, at the bottom of which the phosphine lone-pair electrons are located. The compounds are stable to oxidation by air and hydrolysis. DFT calculations suggested that the… CONTINUE READING