Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases.

摘要: : A TrF2 group (Tr = B, Al, Ga, In, Tl) is placed on one of the α positions naphthalene, and its ability to engage in a triel bond (TrB) with weak (NCH) strong (NC−) nucleophile assessed by ab initio calculations. As competitor, an NH2 neighboring Cα, from which point it forms intramolecular TrB group. The latter internal reduces intensity π-hole Tr atom, decreasing second external TrB. intermolecular weakened factor about two for smaller atoms but less severe larger Tl. can be quite nonetheless; varies minimum 8 kcal/mol NCH base, up as much 70 CN−. Likewise, appearance base like CN− lessens TrB, where such becomes questionable.