Poynder Tiffany B, Chamorro Orué Analia I, Sharp-Bucknall Lachlan, Flynn Matthew T, Wilson David J D, Athukorala Arachchige Kasun S, Clegg Jack K, Dutton Jason L
Department of Chemistry and Physics, La Trobe University, Melbourne, Victoria, 3086, Australia.
School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Queensland 4072, Australia.
Chem Commun (Camb). 2021 May 18;57(40):4970-4973. doi: 10.1039/d1cc01567b.
It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not displace chloride, but rather forms a weak complex with the iodine via halogen bonding along the C-I bond axis. This interaction is interrogated by NMR, structural, charge density, and theoretical investigations, which all indicate that pyridine does not activate PhICl2 as proposed.
此前有人提出,吡啶可以通过取代一个氯原子并形成[PhI(Pyr)(Cl)]+阳离子作为反应中间体来激活PhICl2。在这里我们表明,吡啶不会取代氯,而是通过沿着C-I键轴的卤键与碘形成弱络合物。通过核磁共振、结构、电荷密度和理论研究对这种相互作用进行了探究,所有这些研究都表明吡啶并不会如所提出的那样激活PhICl2。