Ab initio calculations are used to provide information on H(3)N...XY...HF triads (X, Y=F, Cl, Br) each having a halogen bond and hydrogen bond. The investigated include H(3)N...Br(2)-HF, H(3)N...Cl(2)...HF, H(3)N...BrCl...HF, H(3)N...BrF...HF, H(3)N...ClF...HF. To understand the properties of systems better, corresponding dyads also investigated. Molecular geometries, binding energies, infrared spectra monomers, dyads, studied at MP2 level theory with 6-311++G(d,p) basis set. Because primary...

A single-electron tetrel bond was predicted and characterized in FXH₃⋯CH₃ (X = C, Si, Ge, Sn) complexes.

An ab initio study of the complexes formed by hypohalous acids (HOX, X = F, Cl and Br) with formaldehyde has been carried out at MP2/aug-cc-pVTZ computational level. Two minima are found, one an H⋯O contact other X⋯O contact. The former is more stable than latter, strength difference between them decreases as size atom increases. associated HO XO bonds undergo a bond lengthening red shift, whereas blue shift was observed in acid not involved interaction. interaction properties both analyzed...

A tetrel–hydride interaction was predicted and characterized in the complexes of XH3F···HM (X = C, Si, Ge, Sn; M Li, Na, BeH, MgH) at MP2/aug-cc-pVTZ level, where XH3F HM are treated as Lewis acid base, respectively. This new analyzed terms geometrical parameters, energies, spectroscopic characteristics complexes. The strength is essentially related to nature X groups, with both larger atomic number increased reactivity giving rise a stronger interaction. exhibits similar substituent effects...

The complexes of XH3F⋯N3−/OCN−/SCN− (X = C, Si, Ge, and Sn) have been investigated at the MP2/aug-cc-pVTZ(PP) level. σ-hole X atom in XH3F acts as a Lewis acid forming tetrel bond with pseudohalide anions. Interaction energies these vary from −8 to −50 kcal/mol, mainly depending on nature Charge transfer N/O/S lone pair X–F X–H σ* orbitals results stabilization complexes, former orbital interaction is responsible for large elongation length remarkable red shift its stretch vibration....

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- strong-oxidant-free strategy provides facile approach to great variety organophosphinates thiophosphates. The simple reaction system, good functional-group tolerance, broad substrate scope enable application this method modification natural products direct synthesis bioactive molecules flame retardants.

The development of high-efficiency electrocatalysts for hydrogen evolution reduction (HER)/oxygen (OER) is highly desirable. In particular, metal borides have attracted much attention because their excellent performances. this study, we designed a series by doping transition (TM) in C3B monolayer and further explored potential applications HER/OER via density functional theory (DFT) calculations machine learning (ML) analysis. Our results revealed that the |ΔG*H| values Fe-, Ag-, Re-,...

A pnicogen–hydride interaction has been predicted and characterized in FH2P–HM FH2As–HM (M = ZnH, BeH, MgH, Li, Na) complexes at the MP2/aug-cc-pVTZ level. For analyzed here, P(As) HM are treated as a Lewis acid base, respectively. This is moderate or strong since, for strongest of FH2As–HNa complex, energy amounts to −24.79 kcal/mol, binding distance equal about 1.7 Å, much less than sum corresponding van der Waals radii. By comparison with some related systems, it concluded that...

Abstract Quantum chemical calculations have been performed to study the complex of MCN‐LiCN‐XCCH (M = H, Li, and Na; X Cl, Br, I). The aim is cooperative effect between halogen bond lithium bond. alkali metal has an enhancing on bond, making it increased by 77 94% for Li Na, respectively. There cooperativity former a larger latter, being in range 11.7–29.4%. dependent type atoms. mechanism analyzed views with orbital interaction, charge transfer, dipole moment, polarizability, atom charges,...

The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength bond relative to hydrogen in H(2)CS-HOX (X = F, Cl, Br) system by means quantum chemical calculations. It has been shown that with comparison H(2)CO, S electron donor H(2)CS results a smaller difference Cl corresponding bond, Br is even stronger than bond. Li atom LiHCS methyl group MeHCS cause an increase bonding bonding, but former...

In the present paper, a new type of lithium bonding complex HMgHLiX (X = H, OH, F, CCH, CN, and NC) has been predicted characterized. Their geometries (C(infinityv)) with all real harmonic vibrational frequencies were obtained using second-order Møller-Plesset perturbation theory (MP2) 6-311++G(d,p) basis set. For each complex, bond is formed between negatively charged H atom an HMgH molecule positively Li LiX molecule. Due to formation complexes, Mg-H Li-H bonds are elongated....

Abstract The σ‐hole tetrel bond in pyrazine/1,4‐dicyanobenzene⋅⋅⋅TH 3 F (T=C and Si) the π‐hole pyrazine/1,4‐dicyanobenzene⋅⋅⋅F 2 TO have been compared. is stronger than corresponding bond, with a larger interaction energy, shorter binding contact, greater electron density, bigger charge transfer. Pyrazine forms more stable tetrel‐bonded complex 1,4‐dicyanobenzene even though nitrogen atom former has smaller negative electrostatic potential latter. An interesting cooperative effect was found...

Hydrogen-bonded clusters, H(3)C-HCN, HCN-HCN, H(3)C-HCN-HCN, H(3)C-HNC, HNC-HNC, and H(3)C-HNC-HNC, have been studied by using ab initio calculations. The optimized structures, harmonic vibrational frequencies, interaction energies are calculated at the MP2 level with aug-cc-pVTZ basis set. cooperative effects in properties of these complexes investigated quantitatively. A cooperativity contribution around 10% relative to total energy was found H(3)C-HCN-HCN complex. In case H(3)C-HNC-HNC...

Abstract We designed M 1 ⋅⋅⋅C 6 H 5 X⋅⋅⋅HM 2 (M =Li + , Na ; X=Cl, Br; =Li, Na, BeH, MgH) complexes to enhance halogen–hydride halogen bonding with a cation–π interaction. The interaction strength has been estimated mainly in terms of the binding distance and energy. results show that is strengthened greatly by energy triads two six times as much dyads. largest −8.31 kcal mol −1 for bond Li Br⋅⋅⋅HNa complex. nature cation, donor, metal hydride influence bond. enhancement effect on larger...

Using ab initio calculations, we have studied the structures, properties, and nature of halogen bonds in H2CS–XY (XY = FF, ClF, ClCl, BrF, BrCl, BrBr) complexes. The results show that ring-shaped complexes are formed by a bond (S···X) secondary hydrogen (H···X). We also analyzed H2CS–ClF–ClF FCl–H2CS–ClF to investigate cooperative diminutive bonding. effect bonding is found former, while present latter. finally considered solvent on H2CS–BrCl complex has prominent enhancing it. been with...

Abstract The interplay between pnicogen bonds and cation–π interactions has been investigated at the MP2/aug‐cc‐pVDZ level. Interesting cooperative diminutive effects are observed when coexist in same complex. These have analyzed terms of structural, energetic, charge‐transfer properties complexes. variations electron density critical points intermolecular bond used to analyze strengthening or weakening. nature mechanisms studied by means symmetry‐adapted perturbation theory molecular...

MP2/aug-cc-pVTZ calculations have been performed on π-hole triel- and chalcogen-bonded complexes involving a heteroaromatic compound. These are very stable with large interaction energy up to -47 kcal mol-1. The sp2-hybridized nitrogen atom engages in stronger bond than the sp-hybridized species although former has smaller negative electrostatic potential. oxygen 1,4-benzoquinone is weaker electron donor atom. triel chalcogen bond. A clear structural deformation found for or molecule these...