Phys. Chem. Chem. Phys. 13, 13951-13961 (2011)

DOI: 10.1039/C1CP20480G

An ab initio study of cooperative effects in ternary complexes X:CNH:Z with X, Z=CNH, FH, ClH, FCl, and HLi: structures, binding energies, and spin-spin coupling constants across intermolecular bonds
 
A systematic ab initio investigation has been carried out to determine the structures, binding energies, and spin–spin coupling constants of ternary complexes X:CNH:Z and corresponding binary complexes X:CNH and CNH:Z, for X, Z = CNH, FH, ClH, FCl, and HLi. The enhanced binding energies of ternary complexes X:CNH:Z for fixed X as a function of Z decrease in the same order as the binding energies of the binary complexes CNH:Z. In contrast, the enhanced binding energies of the ternary complexes for fixed Z as a function of X do not decrease in the same order as the binding energies of the binary complexes X:CNH, a consequence of the increased stabilities of ternary complexes FCl:CNH:Z due to very strong chlorine-sharedhalogen bonds. For complexes in which the XCNH interaction is a D–HC hydrogen bond for D–H the proton–donor group (N–H, F–H, or Cl–H), spin–spin coupling constants 1J(D–H) and 2hJ(D–C) in ternary complexes X:CNH:Z decrease in absolute value as the binding energies of binary complexes CNH:Z and the enhanced binding energies of the ternary complexes for fixed X as a function of Z also decrease. However, 2XJ(F–C) increases as the enhanced binding energies of the ternary complexes FCl:CNH:Z decrease, a consequence of the nature of the chlorine-shared halogen bond. The one-bond coupling constants 1J(N–H) for the CNHZ interaction in ternary complexes vary significantly, depending on the nature of the XCNH interaction. The largest values of 1J(N–H) are found for ternary complexes with FCl as X. Two-bond coupling constants 2hJ(N–A) for A the proton-acceptor atom of Z, and 2dJ(N–H) decrease in absolute value in the order of decreasing enhancement energies of ternary complexes X:CNH:Z for fixed Z as a function of X.