The interplay between cation–π and coinage‐metal–oxygen interactions are investigated in the ternary systems N???PhCCM???O (N=Li+, Na+, Mg2+; M=Ag, Au; O=water, methanol, ethanol). A synergetic effect is observed when cation–π and coinage‐metal–oxygen interactions coexist in the same complex. The cation–π interaction in most triads has a greater enhancing effect on the coinage‐metal–oxygen interaction. This effect is analyzed in terms of the binding distance, interaction energy, and electrostatic potential in the complexes. Furthermore, the formation, strength, and nature of both the cation–π and coinage‐metal–oxygen interactions can be understood in terms of electrostatic potential and energy decomposition. In addition, experimental evidence for the coexistence of both interactions is obtained from the Cambridge Structural Database (CSD). 相似文献
An ab initio calculation has been carried for the carbene tetrel bonded complexes CH3Y???CH2 (Y = F, CN, NC, and NO2), CH3F???CZ2 (Z = Cl and CH3), XH3F???CF2 (X = C, Si, Ge, and Sn), SiF4???CF2, and XH3F???NHC (N-heterocyclic carbene), where carbene is treated as a Lewis base and XH3Y is a Lewis acid. Formation of the tetrel bond is mainly attributed to charge transfer from the lone pair on the C atom in the carbene toward the σ* X–Y orbital and also the σ* X–H one in the strong tetrel bond. The carbene tetrel bond is strengthened/weakened by the electron-withdrawing group in the tetrel donor/acceptor and enhanced by the methyl group in C(CH3)2. NHC forms a stronger carbene tetrel bond in XH3F???NHC (X = Si, Ge, and Sn) where it exceeds that of the majority of H-bonds. Interestingly, the tetrel bond becomes stronger in the order of X = C < Ge < Sn < Si in XH3F???NHC and the largest interaction energy occurs in SiH3F???NHC, amounting to ?103 kJ/mol. The carbene tetrel bond can be strengthened by cooperative effect with the N???M interaction in trimers H2C???CH3CN???M (M = CH3CN, HCN, ICN, SbH2F, LiCN, and BeH2) and has doubled in H2C???CH3CN???BeH2.
Ab initio calculations have been performed for the complexes of benzene with HArF, HKrF, and HXeF. The computed results indicate that the complexes of benzene-HArF exist in different conformations and among them those with π-hydrogen bonds are the more stable than those with C-H···F hydrogen bonds. Interestingly, the Ar-H stretching frequency is redshifted in the more stable isomer and blueshifted in the less stable form. The Ng (Ng=Ar, Kr, and Xe) atomic number dependence of the Ng-H···π and C-H···F hydrogen bonds has been explored. The result indicates that the strength of Ng-H···π and C-H···F hydrogen bonds is weakened with the increase of Ng atomic number. Natural bond orbital analysis has been performed to understand the interaction nature, frequency shift of H-Ng stretch, and dependence of Ng-H···π and C-H···F hydrogen bonds on the Ng atomic number. 相似文献
CH3Li–FArH–X (X?=?H2, OC, N2, P2, CO2, CO, BeH2) trimers have been investigated using quantum chemical calculations at the QCISD/6-311++G(2d,2p) level. The results show that the lithium bonding has a prominent effect on the strength and properties of the hydrogen bonding. The hydrogen-bonding interaction energy is increased by 160–340% due to the presence of lithium bonding. The Ar–H stretch vibration shows a blue shift in the FArH–X (X?=?H2, OC, N2, CO2, CO) dimer, but a red shift in the FArH–X (X?=?P2, BeH2) dimer. The red shift is increased in the corresponding trimer, while the blue shift shows a different change. The blue shift is also increased in CH3Li–FArH–X (X?=?H2, OC, N2, CO2) trimers, but it changes to a red shift in the CH3Li–FArH–CO trimer. The shift change is consistent with the explanation given by Joseph and Jemmis. 相似文献
Ab initio calculations are used to provide information on H3N???XY???HF triads (X, Y=F, Cl, Br) each having a halogen bond and a hydrogen bond. The investigated triads include H3N???Br2‐HF, H3N???Cl2???HF, H3N???BrCI???HF, H3N???BrF???HF, and H3N???ClF???HF. To understand the properties of the systems better, the corresponding dyads are also investigated. Molecular geometries, binding energies, and infrared spectra of monomers, dyads, and triads are studied at the MP2 level of theory with the 6‐311++G(d,p) basis set. Because the primary aim of this study is to examine cooperative effects, particular attention is given to parameters such as cooperative energies, many‐body interaction energies, and cooperativity factors. The cooperative energy ranges from ?1.45 to ?4.64 kcal mol?1, the three‐body interaction energy from ?2.17 to ?6.71 kcal mol?1, and the cooperativity factor from 1.27 to 4.35. These results indicate significant cooperativity between the halogen and hydrogen bonds in these complexes. This cooperativity is much greater than that between hydrogen bonds. The effect of a halogen bond on a hydrogen bond is more pronounced than that of a hydrogen bond on a halogen bond. 相似文献
In this paper, the cooperative effect of halogen bond with hydrogen bond has been used to make a halogen bond in FCl-CNH dimer vary from a chlorine-shared one to an ion-pair one. The halogen bond is strengthened in FCl-CNH-CNH trimer and its maximal interaction energy equals to -76 kJ∕mol when the number of CNH in FCl-CNH-(CNH)(n) polymer approaches infinity. Once the free H atom in FCl-CNH-CNH trimer is replaced with alkali metals, the halogen bond becomes strong enough to be an ion-pair one in FCl-CNH-CNLi and FCl-CNH-CNNa trimers. An introduction of a Lewis acid in FCl-CNH dimer has a more prominent effect on the type of halogen bond. A prominent cooperative effect is found for the halogen bond and hydrogen bond in the trimers. FH-FCl-CNH-CNH and FH-FCl-CNH-CNLi tetramers have also been studied and the interaction energy of halogen bonding in FH-FCl-CNH-CNLi tetramer is about 12 times as much as that in the FCl-CNH dimer. The atoms in molecules and natural bond orbital analyses have been carried out for these complexes to understand the nature of halogen bond and the origin of the cooperativity. 相似文献
High quantum chemical calculations have been performed for binary complexes of MCN···ZX3 (M = Cu, Ag, Au; Z = B, Al; X = H, F) and C2H4···AlX3. The strength of triel bonding depends on the nature of triel and coin metal atoms as well as the F substituents and electron donors. The molecular electrostatic potential (MEP) analysis confirms a σ‐hole at the M‐C bond end of MCN, engaging in a regium bond with C2H4 in an increasing sequence of AgCN < CuCN < AuCN. The complex C2(CN)4···AuCN is unstable in view of MEPs, but a big attractive interaction energy (?38 kcal/mol) is produced when both molecules approach, which is mainly caused by polarization including orbital interactions. Both types of interactions are strengthened in ternary complex of C2H4···MCN···ZX3 but are weakened in NCAu···C2H4···AlX3 and C2(CN)4···AuCN···ZH3. It is found that the variation from synergistic to diminutive effects can be modulated by four CN groups in C2(CN)4. Interestingly, the binding distances of both interactions have an unexpected change. The cooperativity of both interactions has been explained with MEP and charge transfer. When C2H4 binds with AlX3 or AuCN, its π electron density is greatly decreased and even its MEP becomes positive, but it is still able to participate in a regium bond or a triel bond. 相似文献
Ab initio calculations at the MP2/aug-cc-pVTZ level have been performed to study the cooperativity of hydrogen bonds in homoclusters
(HNC–HNC–HNC and HNC–HNC–HNC–HNC) and heteroclusters (H3N–HNC–HNC and H3N–HNC–HNC–HNC). The cooperative energies in the HNC–HNC–HNC and H3N–HNC–HNC trimers are –2.05 and –2.56 kcal/mol, respectively. The result shows that the cooperativity in the heterotrimer
is larger than that in the homotrimer. A similar result also happens in the tetramers. The energy decomposition scheme indicates
that orbital interaction is a major contribution to the cooperative energy of N···HN hydrogen bond, whereas the electrostatic
and orbital interactions to that of C···HN hydrogen bond. The effect of HNC chain length on the strength of N···HN hydrogen
bond has also been considered at the MP2/aug-cc-pVDZ level. It is indicated that the interaction energy of N···HN hydrogen
bond trends to be a fixed value when the HNC number tends to be infinite, and the strength of N···HN hydrogen bond is regulated
mainly through the electrostatic and polarization interactions although the charge transfer interaction also has an effect
on it. 相似文献
In this article, we performed quantum chemical calculations to study the π Au-bond in the HCCH···AuX (X = OH, F, Cl, Br, CH(3), CCH, CN, and NC) system. For comparison, we also investigated the HCCH···Au(+) and H(2)CCH(2)···AuF complexes. The equilibrium geometries and infrared spectra at the MP2 level were reported. The interaction energies were calculated at the MP2 and coupled-cluster single double triple levels. The natural bond orbital results support the Dewar-Chatt-Duncanson model. Moreover, we focused on the influence of X atom on the geometries, interaction energies, and orbital interactions as well as the comparison between HCCH···AuF and H(2)CCH(2)···AuF complexes. Although the π Au-bond in these complexes is electrostatic in nature, the weight of covalent nature is also important. 相似文献