Complicated synergistic effects have been found between metal–π interaction and halogen bond in the complexes FCCF⋯MCCX⋯NCH (M = Li, Cu, Ag, and Au; X = Cl, Br, and I).
The hydrogen-bonded complexes formed of superhalogen MX2NY (M = Li, Na; N = Be, Mg; X, Y = F, Cl, Br) and hydrogen fluoride have been investigated with quantum chemical calculations at the MP2/aug-cc-pVDZ and M06-2X/aug-cc-pVDZ levels of theory. It was shown that the M06-2X method presents similar results with the MP2 method. The strength of hydrogen bonding is related with the nature of metal and halogen atoms. The metal with greater electron-donating ability leads to a stronger hydrogen bond, whereas the halogen with bigger electron-withdrawing ability also results in the stronger hydrogen bond. The presence of hydrogen bond has a small effect on the structures of the superhalogen and contributes to the stability of the superhalogen.
Based on the idea of environmental friendliness, we first studied the hydrothiolation reactions of thiophenol with allylamine using a green catalyst─an external electric field (EEF). The hydrothiolation reactions could occur through Markovnikov addition (path M) and anti-Markovnikov addition (path AM) pathways. The calculation results demonstrated that when the EEF was oriented along F–X, F–Y, and F+Z directions, path M was accelerated. However, it is favorable for path AM only when the EEF is oriented along the +X and −Y-axes. In addition, the introduction of the EEF further increased and lowered the differences of the reaction barrier as the EEF was oriented along F–X, F–Y, and F+X directions. The solvent effects were also considered in this work. Hopefully, this unprecedented and green catalytic method for the hydrothiolation reactions of allylamine may provide guidance in the lab.
Ternary systems H3N⋯FH2X⋯MCN (X = P and As; M = Cu, Ag, and Au) as well as the corresponding pnicogen-bonded and coordination-bonded binary systems have been studied.
Abstract Quantum chemical calculations have been performed on six halogen–hydride halogen bonded complexes with F3CCl or F3CBr as the halogen donor and metal hydride (HLi, HBeH and HMgH) as the halogen acceptor. At the MP2/6-311++G(d,p) level, the interaction strength spans from 2.62 to 17.68 kJ mol–1. The C–Cl and C–Br bonds are contracted. However, no evident blue shift accompanies this contraction. The H–Li bond is also contracted, but the H–He and H–Mg bonds are lengthened. However, a blue shift occurs for all these bond-stretching vibrations. These properties were analysed using the theory of natural bond orbital (NBO) and atoms in molecules (AIM). A symmetry-adapted perturbation theory (SAPT) analysis was also carried out to unveil the nature of this novel interaction. It is demonstrated that the electrostatic interaction plays a main role in the interaction, although induction and dispersion interactions are also important. Keywords: halogen–hydride halogen bondblue shiftdihydrogen bondσ–hole interactionsymmetry-adapted perturbation theory Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant No. 20973149). It was also supported, in part, by an open project of the State Key Laboratory of Supramolecular Structure and Materials (SKLSSM200909), Jilin University, China.
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