Pnicogen Bonds Research Articles

Participation of transition metal atoms in noncovalent bonds.

The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and many of their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M⋯N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.

Ab initio investigation of the competition of pnicogen, halogen, and hydrogen bonds resulting from the interactions between cyanophosphine and hypohalous acids.

The complexes formed as a result of the interactions between cyanophosphine (CP, H2PCN) and hypohalous acid molecules (HOX, X = F, Cl, Br, and I) were studied by employing ab initio computations conducted at the MP2/aug-cc-pVTZ level. Three types of complexes were acquired (I, II, and III) as a result of the (O∙∙∙P) pnicogen bond, the (N∙∙∙H) hydrogen bond, and the (N∙∙∙X) halogen bond interaction, respectively. The results of harmonic vibrational frequency calculations with no imaginary frequencies confirmed the structures as minima. In addition, given the interaction energy of the complexes, hydrogen bond complexes of structure II have the highest stability compared to other structures. In all studied complexes, the strength of the interactions depended on the electronegativity of the halogen atoms. The characteristics and nature of the whole three types of complexes were examined and evaluated with natural bond orbital (NBO), atom in molecules (AIM), molecular electrostatic potential (MEP) maps, non-covalent interaction (NCI) index, and electron density difference (EDD) analyses. The optimization of all complexes and corresponding monomers was conducted through the ab initio method, employing the MP2 level along with the aug/cc-pVTZ basis set for all atoms, except for the iodine (I) atom, for which the aug-cc-pVTZ (PP) basis set was employed. Subsequent frequency calculations were executed to ascertain the minimum energy state of the complexes at the MP2 level and the aug/cc-pVTZ basis set, utilizing Gaussian09 software. The MEP maps of the monomers were generated using the analysis-surface suite (WFA-SAS) software package. To probe the orbital interactions within the studied complexes, NBO analysis was performed employing NBO software. The assessment of bond nature, topological features, and electron density values at critical points for the studied complexes was undertaken using AIMAll software. The NCI index was derived utilizing Multiwfn software, and its three-dimensional representation was rendered using VMD software.

Interplay of Hydrogen, Pnicogen, and Chalcogen Bonding in X(H2O)n=1-5 (X = NO, NO+, and NO-) Complexes: Energetics Insights via a Molecular Tailoring Approach.

Nitric oxide (NO) and its redox congeners (NO+ and NO-), designated as X, play vital roles in various atmospheric and biological events. Understanding the interaction between X and water is inevitable to explain the different reactions that occur during these events. The present study is a unified attempt to explore the noncovalent interactions in microhydrated networks of X using the MP2/aug-cc-pVTZ//MP2/6-311++G(d,p) level of theory. The interactions between X and water have been probed by the molecular electrostatic potential (MESP) by exploiting the features of the most positive (Vmax) and most negative potential (Vmin) sites. The individual energy and cooperativity contributions of various types of noncovalent interactions present in X(H2O)n=1-5 complexes are estimated with the help of a molecular tailoring-based approach (MTA-based). The MTA-based analysis reveals that among various possible interactions in NO(H2O)n complexes, the water···water hydrogen bonds (HBs) are the strongest. Neutral NO can form hydrogen and pnicogen bonds (PBs) with water depending on the orientation; however, such HBs and PBs are the weakest. On the other hand, in the NO+(H2O)n complexes, the NO+···water interactions that occur through PBs are the strongest; the next one is the chalcogen bonding (CB), and the water···water HBs are the weakest. In the case of the NO-(H2O)n complexes, the HB interactions via both N and O atoms of NO- and water molecules are the strongest ones. The strength of water···water HB interactions is also seen to increase with the increase in the number of water molecules in NO-(H2O)n. The present study exemplifies the applicability of MTA-based calculations for quantifying various types of individual noncovalent interactions and their interplay in microhydrated networks of NO and its related ions.

Influence of Internal Angular Arrangement on Pnicogen Bond Strength.

The three Z-X covalent bonds of a ZX3 unit (Z = P, As, Sb, Bi) are normally arranged in a pyramidal structure. Quantum chemical calculations show that pnicogen bonds (ZBs) to the central Z are weakened if ZX3 is flattened, as in the opening of an umbrella. The partial closing of the umbrella has the opposite effect of substantially strengthening these ZBs, even amounting to a 2- or 3-fold magnification in certain cases. The strongest such bonds, wherein Sb and Bi are in a strained configuration within a ZO3CH model system, have interaction energies of 20 kcal/mol with an NH3 base. Most of these systems, whether flattened or more pyramidal, are capable of engaging in three ZBs simultaneously, despite a certain amount of negative cooperativity.

Unraveling pnicogen bonding cooperativity: Insights from molecular electrostatic potential analysis.

A theoretical investigation on the cooperativity of a series of binary, ternary, and quaternary complexes interconnected by pnicogen bonds has been conducted using calculations at the M06-2X/aug-cc-pVTZ level of density functional theory. By measuring changes in the molecular electrostatic potential (MESP) at the nucleus of interacting atoms in all of the complexes, it is possible to quantify the substantial reorganization of the electron density triggered by the formation of pnicogen bonds. The positive change in MESP, indicating a loss of electron density from the donor molecule in a dimer, facilitates the acceptance of electron density from a third molecule, resulting in the formation of a ternary complex with a stronger pnicogen bond compared to the one present in the binary complex. Similarly, the acceptor molecule in a dimer with a negative change in MESP showed an enhanced tendency to donate electron density to an electron-deficient third molecule. The MESP analysis provided valuable insights into the donor/acceptor characteristics of pnicogen bonds within the quaternary complexes. The proposed MESP hypotheses are consistent with the positive cooperativity observed in the pnicogen-bonded clusters. To quantify the changes in MESP, both at the donor atom (ΔVdonor ) and the acceptor atom (ΔVacceptor ), for all pnicogen bonds in the cluster, the total change in MESP (ΔΔVn ) was measured as ΔΔVn = ∑(ΔVdonor )-∑(ΔVacceptor ). Remarkably, ΔΔVn exhibited a strong linear relationship with the sum of the bond energies of the pnicogen bonds in the cluster. This establishes the MESP analysis as a robust approach for understanding the strength and cooperative behavior of pnicogen-bonded clusters. Additionally, the MESP features provided clear evidence of pnicogen bond formation, further supporting the reliability of this approach.

Transition between the Noncovalency and Covalency of σ-Hole Bonds.

The properties of the bond between a N-ligand and a Lewis acid containing a σ-hole are studied by quantum chemical methods. Interactions considered include pnicogen bonds involving SbX5, PX5, and PX3, where X represents any of the halogen atoms F, Cl, Br, or I. Also studied are the tetrel bonds of PbX4 and SiX4, as well as the chalcogen bond involving TeOX4. Both NH3 and NCH are applied as two possible bases of differing potency. Some of the bonds are very strong with interaction energies easily exceeding 25 kcal/mol and with AIM bond critical point densities much higher than 0.04 au, suggesting their classification as coordinate covalent bonds. The pentavalent SbX5 and PX5 fall into this category when combined with NH3, as does TeOX4. Although the tetrel bonds involving PbX4 are only slightly weaker, they are probably better viewed as a strong noncovalent bond on the cusp of covalency. Changing the internal bonding of hypervalent SbX5 to the more conventional SbX3 weakens the interaction to a classical noncovalent pnicogen bond. Reducing the base nucleophilicity from NH3 to NCH weakens the bonds so that they are clearly noncovalent.

Computational analyses of cooperativity between pnicogen and halogen bonds in H2FP:pyrimidine: ClF complex

Computational analyses of cooperativity between pnicogen and halogen bonds in H2FP:pyrimidine: ClF complex

Influence of Internal Noncovalent Bonds on Rotational Dynamics.

While a good deal of information has accumulated concerning the manner in which an intramolecular noncovalent bond can affect the relative energies of various conformers, less is known about how such bonds might affect the dynamics of interconversion between them. A series of molecules are constructed in which symmetrically equivalent conformers containing a noncovalent bond can be interconverted by a bond rotation, the energy barrier to which is computed by quantum chemical methods. The rotation of a CF3 group attached to a phenyl ring is speeded up if a Se··F chalcogen bond can be formed with a SeH or SeF group placed in an ortho position, a bond that is present in and stabilizes the rotational transition state. The analogous SnF3 group can, on the other hand, engage in a Sn··Se tetrel bond in its global minimum. The energetic cost of breakage of this bond is not fully compensated by the appearance of a Se··F chalcogen bond in the rotational transition state. Other systems were designed by placing two phenyl rings on opposite ends of an octahedrally disposed SeF4 group. A high barrier inhibits their rotation with bulky Br atoms in ortho positions, but this barrier is lowered if Br is replaced by groups that can engage in either chalcogen (SeH or SeF) or pnicogen (AsH2) bonds with the F atoms in the rotational transition state. The barrier reduction is closely related to the strength of these noncovalent bonds.

CO2-NH3 dimers: Dominance of π-hole driven tetrel bonding over hydrogen bonding

The presence of a π-hole driven OC…N tetrel bond sustaining the most stable geometry of heterodimers of NH3 with CO2 is evidenced by matrix isolation infrared spectroscopy in combination with quantum chemical computations. The co-existence of a weak H-N…O pnicogen bond alongside the tetrel bond is revealed during the analysis of the electronic structure of heterodimer. Intriguing behaviour of nitrogen in ammonia is observed: i) its very weak electrophilicity ii) its nucleophilic role apparently being independent of the orientation of its non-bonding electron pair.

Comparison of the Ability of N-Bases to Engage in Noncovalent Bonds.

The lone pair of the N atom is a common electron donor in noncovalent bonds. Quantum calculations examine how various aspects of the base on which the N is located affect the strength and other properties of complexes formed with Lewis acids FH, FBr, F2 Se, and F3 As that respectively encompass hydrogen, halogen, chalcogen, and pnicogen bonds. In most cases the halogen bond is the strongest, followed in order by chalcogen, hydrogen, and pnicogen. The noncovalent bond strength increases in the sp<sp2 <sp3 order of hybridization of N. Replacement of H substituents on the base by a methyl group or substituting N by C atom to which the base N is attached, strengthens the bond. The strongest bonds occur for trimethylamine and the weakest for N2 .

The influence of N⋯π pnicogen bonding in π-stacked parallel displaced geometry of nitrobenzene dimers: Evidence using matrix isolation infrared spectroscopy and ab initio computations

The present study elucidates the preferential stabilization of parallel displaced geometry of nitrobenzene dimers by co-operative action of π…π interactions and ON⋯π pnicogen bonding. The homodimers have also been synthesized within Ne and Ar matrixes at cryogenic temperatures followed by their characterization using infrared spectroscopy. The significant contribution of short-range dispersion forces in stabilization of parallel-displaced geometries causes a concomitant rise in Pauli repulsion effects, owing to increased electron correlation. This destabilization is efficiently compensated for, by the added electrostatic effects due to the π-hole facilitated ON⋯π pnicogen bond. The directional determinism of the pnicogen bond proves pivotal in facilitating this co-operation with π…π interactions. These inferences have been obtained by a comparative computational analysis of the parallel displaced and ‘T-shaped’ geometries of the benzene homodimer, with their nitrobenzene analogues.

Pd and Pt metal atoms as electron donors in σ-hole bonded complexes.

Quantum calculations provide a systematic assessment of the ability of Group 10 transition metals M = Pd and Pt to act as an electron donor within the context of pnicogen, chalcogen, and halogen bonds. These M atoms are coordinated in a square planar geometry, attached to two N atoms of a modified phenanthrene unit, as well as two ligand atoms Cl, Br, or I. As the Lewis acid, a series of AFn molecules were chosen, which could form a pnicogen bond (A = P, As, Sb), chalcogen bond (A = S, Se, Te) or halogen bond (A = Cl, Br, I) with M. These noncovalent bonds are fairly strong, varying between 6 and 20 kcal mol-1, with the occupied dz2 orbital of M acting as the origin of charge transferred to the acid. Pt forms somewhat stronger bonds than Pd, and the bond strength rises with the size of the A atom of the acid. Within the context of smaller A atoms, the bond strength rises in the order pnicogen < chalcogen < halogen, but this distinction vanishes for the fifth-row A atoms. The nature of the ligand atoms on M has little bearing on the bond strength. Based on the Harmonic Oscillator Model of Aromaticity (HOMA) index, the ZB, YB and XB bonds were shown to have only a subtle effect on the ring electronic structures.

Heavy pnicogen atoms as electron donors in sigma-hole bonds.

DFT calculations evaluate the strength of σ-hole bonds formed by ZH3 and ZMe3 (Z = N, P, As, Sb) acting as electron donor. Bond types considered include H-bond, halogen, chalcogen, pnicogen, and tetrel bond to perfluorinated Lewis acids FH, FBr, F2Se F3As, F4Ge, respectively, as well as their monofluorinated analogues. All of the Z atoms can engage in bonds of at least moderate strength, varying from 3 to more than 40 kcal mol-1. In most cases, N forms the strongest bonds, but the falloff from P to Sb is quite mild. However, this pattern is not characteristic of all cases, as for example in the halogen bonds, where the heavier Z atoms are comparable to, or even stronger than N. Most of the bonds are strengthened by replacing the three H atoms of ZH3 by methyl groups, better simulating the situation that would be generally encountered. Structural and NMR shielding data ought to facilitate the identification of these bonds within crystals or in solution.

Revisiting conventional noncovalent interactions towards a complete understanding: from tetrel to pnicogen, chalcogen, and halogen bond.

Typical noncovalent interactions, including tetrel (TtB), pnicogen (PniB), chalcogen (ChalB), and halogen bonds (HalB), were systematically re-investigated by modeling the N⋯Z interactions (Z = Si, P, S, Cl) between NH3 - as a nucleophilic, and SiF4, PF3, SF2, and ClF - as electrophilic components, employing highly reliable ab initio methods. The characteristics of N⋯Z interactions when Z goes from Si to Cl, were examined through their changes in stability, vibrational spectroscopy, electron density, and natural orbital analyses. The binding energies of these complexes at CCSD(T)/CBS indicate that NH3 tends to hold tightly most with ClF (-34.7 kJ mol-1) and SiF4 (-23.7 kJ mol-1) to form N⋯Cl HalB and N⋯Si TtB, respectively. Remarkably, the interaction energies obtained from various approaches imply that the strength of these noncovalent interactions follows the order: N⋯Si TtB > N⋯Cl HalB > N⋯S ChalB > N⋯P PniB, that differs the order of their corresponding complex stability. The conventional N⋯Z noncovalent interactions are characterized by the local vibrational frequencies of 351, 126, 167, and 261 cm-1 for TtB, PniB, ChalB, and HalB, respectively. The SAPT2+(3)dMP2 calculations demonstrate that the primary force controlling their strength retains the electrostatic term. Accompanied by the stronger strength of N⋯Si TtB and N⋯Cl HalB, the AIM and NBO results state that they are partly covalent in nature with amounts of 18.57% and 27.53%, respectively. Among various analysis approaches, the force constant of the local N⋯Z stretching vibration is shown to be most accurate in describing the noncovalent interactions.

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models.

Bonding within the AsF3 crystal is analyzed via quantum chemical methods so as to identify and quantify the pnicogen bonds that are present. The structure of a finite crystal segment containing nine molecules is compared with that of a fully optimized cluster of the same size. The geometries are qualitatively different, with a much larger binding energy within the optimized nonamer. Although the total interaction energy of a central unit with the remaining peripheral molecules is comparable for the two structures, the binding of the peripherals with one another is far larger in the optimized cluster. This distinction of much stronger total binding within the optimized cluster is not limited to the nonamer but repeats itself for smaller aggregates as well. The average binding energy of the cluster rises quickly with size, asymptotically approaching a value nearly triple that of the dimer.

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl3-Acetone Heterodimer: Experimental Confirmation at Low Temperatures.

Both tetrel and pnicogen bonds are known to be induced through σ-/π-holes. This work reports computational and experimental evidence of the carbonyl carbon of acetone hosting a tetrel bond by dispersion rather electrostatic forces, for the first time, while phosphorus of POCl3 sustains pnicogen bonding via the σ-hole. Heterodimers of POCl3 with acetone (CH3COCH3) have been isolated within inert gas matrixes of Ar and N2 at 12 K. Characteristic vibrational bands at P═O stretching of POCl3 and C═O stretching of CH3COCH3 have been obtained in support of the computations. The potential energy surface has been traced computationally using ab initio and density functional methods. CH3COCH3 harboring such a tetrel bond, in itself, is quite intriguing. The interplay of these interactions has been comprehended by the quantum theory of atoms in molecules, natural bond orbital, energy decomposition, electrostatic potential mapping, and noncovalent interaction analyses.

The first principle study of chalcogen bonds, pnicogen bond and their mutual effects in a set of complexes between the triazine with SHF and PH2F ligands

In the present study, the strength, nature and cooperativity effects of chalcogen and pnicogen bonds in a set of complexes between the triazine (TA) with SHF and PH2F are investigated at M06-2X/6–311++G (d, p) and CCSD/6–311++G (d, p) levels of theory. According to the results, the absolute values of complexation energies of chalcogen bonded systems are greater than the corresponding pnicogen bonded complexes. The simultaneous presence of two or three non-covalent interactions leads to negative cooperativity effects. Furthermore, the electron density values of chalcogen bonded complexes are more than their pnicogen ones, which emphasizes the stronger interactions in the former systems. Also, the LpN → σ*X-F interaction has been attenuated in the presence of two or three interactions, which is attributed to the presence of negative cooperativity effects. Finally, the aromaticity indices values show with an increase in the number of non-covalent interactions, the TA ring aromaticity character is decreased.

Unique O═N...O Pnicogen Interactions in Nitromethane Dimers: Evidence Using Matrix Isolation Infrared Spectroscopy and Computational Methodology.

Geometries of nitromethane homodimers have been revisited using ab initio and density functional methodologies, following their formation within cryogenic matrices, confirmed using infrared spectroscopy. In contrast to the claim that the intermolecular interactions are due to dispersion forces or very weak hydrogen bonds, in the present work, concrete evidence for the prevalence of O═N...O pnicogen bonding has been presented. The pnicogen bonds have been found to be primarily responsible for the characteristic geometry of a homodimer. The formation of a nitromethane dimer with pnicogen bonding stabilization is evidenced using matrix isolation infrared spectroscopy with Ne and Ar matrices and computations. The interactions within homodimers have been characterized using quantum theory of atoms in molecules, natural bond orbital, energy decomposition, electrostatic potential mapping, and noncovalent interaction analyses. The larger intermolecular separations in liquid nitromethane indicated by previous molecular dynamics-based studies alongside the supposed invariance of infrared spectra in the gas phase and liquid phase could have led to the assumption of a lack of intermolecular interactions. However, the prevalence of hydrogen and pnicogen bonds across these larger than usual separations is affirmed by the geometries presented here.

Competition between Intra and Intermolecular Pnicogen Bonds: Complexes between Naphthalene Derivatives and Neutral or Anionic Bases.

The PnF2 (Pn=P,As,Sb,Bi) on a naphthalene scaffold can engage in an internal pnicogen Pn⋅⋅⋅N bond (PnB) with an NH2 group placed close to it on the adjoining ring. An approaching neutral NH3 molecule can engage in a second PnB with the central Pn, which tends to weaken the intramolecular bond. The presence of the latter in turn weakens the intermolecular PnB with respect to that formed in its absence. Replacement of the external NH3 by a CN- anion causes a fundamental change in the bonding pattern, producing a fourth covalent bond with Pn, which rearranges into a trigonal bipyramidal motif. This addition disrupts the internal Pn⋅⋅⋅N pnicogen bond, recasting the PnF2 ⋅⋅⋅NH2 interaction into an NH⋅⋅⋅F H-bond.

σ-Hole Bonds and the VSEPR Model—From the Tetrahedral Structure to the Trigonal Bipyramid

Complexes linked by various interactions are analysed in this study. They are characterized by the tetrahedral configuration of the Lewis acid centre. Interactions, being a subject of this study, are classified as σ-hole bonds, such as the halogen, chalcogen, pnicogen, and tetrel bonds. In the case of strong interactions, the tetrahedral configuration of the Lewis acid centre changes into the trigonal bipyramid configuration. This change is in line with the Valence-Shell Electron-Pair Repulsion model, VSEPR, and this is supported here by the results of high-level ab initio calculations. The theoretical results concerning the geometries are supported mainly by the Natural Bond Orbital, NBO, method.