Investigation of substituent effects in aerogen-bonding interaction between ZO(3) (Z=Kr, Xe) and nitrogen bases

摘要

The substituent effects in aerogen bond interactions between ZO(3) (Z=Kr, Xe) and different nitrogen bases are studied at the MP2/aug-cc-pVTZ level of theory. The nitrogen bases include the sp bases NCH, NCF, NCCl, NCBr, NCCN, NCOH, NCCH3 and the sp(3) bases NH3, NH2F, NH2Cl, NH2Br, NH2CN, NH2OH, and NH2CH3. The nature of aerogen bonds in these complexes is analyzed by means of molecular electrostatic potential, electron localization function, quantum theory atoms in molecules, noncovalent interaction index, and natural bond orbital analyses. The interaction energy (E-int) ranges from -4.59 to -9.65 kcal/mol in the O(3)ZNCX complexes and from -5.30 to -13.57 kcal/mol in the O(3)ZNH(2)X ones. The dominant charge-transfer interaction in these complexes occurs across the aerogen bond from the nitrogen lone-pair (n(N)) of the Lewis base to the sigma*(Z-O) antibonding orbital of the ZO(3). Besides, the formation of aerogen bond tends to decrease the Kr-83 or Xe-131 chemical shielding values in these complexes. (c) 2016 Wiley Periodicals, Inc.