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Formation of macrocyclic ring systems by carbonylation of trifunctional P/B/B frustrated Lewis pairs.

Long WangShunxi DongConstantin Gabriel DaniliucLei LiuStefan GrimmeRobert KnitschHellmut EckertMichael Ryan HansenGerald KehrGerhard Erker
Published in: Chemical science (2017)
The trifunctional P/B/B frustrated Lewis pairs 11a-c featuring bulky aryl groups at phosphorus [Dmesp (a), Tipp (b), Mes* (c)] react with H2 by heterolytic hydrogen splitting followed by cleavage of HB(C6F5)2 to give the zwitterionic six-membered heterocyclic PH phosphonium/borate products 14a-c. Compounds 11a,b react with carbon monoxide by means of a Lewis acid induced CO insertion/rearrangement sequence that eventually results in the formation of the macrocyclic dimers 17a,b. The respective carbonylation reaction of the Mes*P/B/B FLP gives the macrocyclic trimer 18c. The new products were characterized spectroscopically and by X-ray diffraction and the reaction mechanism was analyzed by DFT calculations.
Keyphrases
  • density functional theory
  • ionic liquid
  • high resolution
  • molecular dynamics simulations
  • electron microscopy
  • crystal structure
  • molecular docking
  • computed tomography
  • dual energy
  • contrast enhanced