π-Hole Triel Bonds between TrPhX2 (Tr = B, Al, Ga; X = F, Cl, Br, CH3, OH) and (BH)2(NHC)2 (NHC = Nitrogen-Heterocyclic Carbene)

Abstract

The π-hole triel bond formed by (BH)2(NHC)2 (NHC denotes nitrogen-heterocyclic carbene) and TrPhX2 (Tr = B, Al, and Ga; X = F, Cl, Br, CH3, and OH) was investigated computationally, with the B=B bond in (BH)2(NHC)2 being the electron donor. A large interaction energy ensures that the complex is quite stable. When the substituent X in the electron acceptor is fixed, the magnitude of the interaction energy varies with the identity of the Tr atom. When Tr is Al or Ga, the interaction energy is stronger than when it is B. With an increase in the electron-withdrawing ability of the substituents, the interaction energy shows distinct changes. When Tr is B or Al, the interaction energy varies as TrPhBr2 > TrPhCl2 > TrPhF2, which is different from the order of their positive electrostatic potentials. When Tr = Ga, the interaction energy hardly changes with an increase in the electronegativity of the halogen atoms. For CH3 and OH substitution, larger interaction energies were obtained, with the interaction energy for the OH substituent being the largest. The main interactions in these systems are a triel bond and an X· ·H hydrogen bond. When the substituents are fixed, the interaction energy of the triel bond increases in the order AlPhX2 < GaPhX2 < BPhX2, which is different from the order of the positive electrostatic potentials on the Tr atom in TrPhX2. When X is a halogen atom, the interaction energy of the triel bond decreases in the order Br > Cl > F, which is opposite to the trend for the positive electrostatic potentials on Tr in TrPhX2. In most complexes, the interaction energy for the hydrogen bond is less than that for the triel bond; there is no hydrogen bond in the methyl-substituted complex. In general, the interaction energy of the hydrogen bonds increases with an increase in the electronegativity of the halogen atoms.