Theoretical Investigation of Hydrogen Bonds between CO and HNF₂, H₂NF, and HNO

Abstract

Ab initio quantum mechanics methods were applied to investigate the hydrogen bonds between CO and HNF2, H2NF, and HNO. We use the Hartree-Fock, MP2, and MP4(SDQ) theories with three basis sets 6-311++G(d,p), 6-311++G(2df,2p), and AUG-cc-pVDZ, and both the standard gradient and counterpoise-corrected gradient techniques to optimize the geometries in order to explore the effects of the theories, basis sets, and different optimization methods on this type of H bond. Eight complexes are obtained, including the two types of C...H-N and O...H-N hydrogen bonds: OC...HNF2(C(s)), OC...H2NF(C(s) and C1), and OC...HNO(C(s)), and CO...HNF2(C(s)), CO...H2NF(C(s) and C1), and CO...HNO(C(s)). The vibrational analysis shows that they have no imaginary frequencies and are minima in potential energy surfaces. The N-H bonds exhibit a small decrease with a concomitant blue shift of the N-H stretch frequency on complexation, except for OC...HNF2 and OC...H2NF(C1), which are red-shifting at high levels of theory and with large basis sets. The O...H-N hydrogen bonds are very weak, with 0 K dissociation energies of only 0.2-2.5 kJ/mol, but the C...H-N hydrogen bonds are stronger with dissociation energies of 2.7-7.0 kJ/mol at the MP2/AUG-cc-pVDZ level. It is notable that the IR intensity of the N-H stretch vibration decreases on complexation for the proton donor HNO but increases for HNF2 and H2NF. A calculation investigation of the dipole moment derivative leads to the conclusion that a negative permanent dipole moment derivative of the proton donor is not a necessary condition for the formation of the blue-shifting hydrogen bond. Natural bond orbital analysis shows that for the C...H-N hydrogen bonds a large electron density is transferred from CO to the donors, but for the O...H-N hydrogen bonds a small electron density transfer exists from the proton donor to the acceptor CO, which is unusual except for CO...H2NF(C(s)). From the fact that the bent hydrogen bonds in OC(CO)...H2NF(C(s)) are quite different from those in the others, we conclude that a greatly bent H-bond configuration shall inhibit both hyperconjugation and rehybridization.

The interfacial modification of rice straw fiber reinforced poly(butylene succinate) composites: Effect of aminosilane with different alkoxy groups

“…Figure 10 showed the FTIR spectra of RSF‐PBS, AEAPTES‐RSF‐PBS, and AEAPTMES‐RSF‐PBS, the stretching band of RSF‐PBS at ∼ 1715 cm −1 was assigned to the carbonyl groups of PBS, while the bands at 1722 and 1731 cm −1 were attributed to hydrogen‐bonded carbonyl groups,33–38 the formation of which caused a blue‐shift 39. The peaks occurring at different locations were assigned to hydrogen‐bonds and double contract hydrogen‐bonds 40–41. Therefore the results indicated that the surface amine of AEAPTES‐ and AEAPTMES‐treated RSF attack the PBS polymer through the hydrogen‐bonds and thus increased the interfacial adhesion.…”

Exploring Host–Guest Interactions in the α-Zn3(HCOO)6 Metal-Organic Framework

“…Previous computational studies showed that both the carbon and oxygen of CO are capable of hydrogen bonding, but a stronger interaction was observed for C···H as compared to O···H. 88,89 Therefore, CO likely interacts with the hydrogens of α-Zn 3 (HCOO) 6 via the carbon atom. Consistent with the apparent 13 C CS parameters, motional simulation results also revealed unidirectional trends in α and β as a function of temperature.…”

Computational investigations of HNO in biology

“…HNO can form various kinds of complexes with non-metal molecules, such as CO [31], HNO [32,33], HOX (X = F, Cl, Br, I) [34], CH 3 X (X = F, Cl, Br) [35], HFSO 2 [36], CH 3 CHO [37], HCONH 2 [38], XCHY (X = H, F, Cl, Br, CH 3 ; Y = O, S) [39], C 2 H 2 [40], HArF [41], and O 3 [42]. Based on the computational investigations, it is interesting to note that in these complexes, as long as the geometries allow, the most stable isomers prefer to involve both the terminal H and O atoms of HNO in the interactions, as illustrated in Fig.…”