How Many Pnicogen Bonds can be Formed to a Central Atom Simultaneously?

Wysokiński, Rafał; Zierkiewicz, Wiktor; Michalczyk, Mariusz; Scheiner, Steve

doi:10.1021/acs.jpca.0c00257

Cited by 30 publications

(24 citation statements)

References 94 publications

(119 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…energy diminishes with larger Z atoms, so that there is a closer competition between the σ and π-hole complex binding energies. Another study of pnicogen bonded systems addressed the question of how many Lewis base ligands can be attached to a single ZF3 molecule [134]. The ZF3 monomer (Z= P, As, Sb, Bi) is characterized by three σ-holes, one opposite each Z-F bond, and a much shallower one that lies directly opposite the Z lone pair, amongst the three F atoms.…”

Section: σ- Hole and π-Hole On The Same Atommentioning

confidence: 99%

Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons

2021

Self Cite

View full text Add to dashboard Cite

Over the last years, scientific interest in noncovalent interactions based on the presence of electron-depleted regions called σ-holes or π-holes has markedly accelerated. Their high directionality and strength, comparable to hydrogen bonds, has been documented in many fields of modern chemistry. The current review gathers and digests recent results concerning these bonds, with a focus on those systems where both σ and π-holes are present on the same molecule. The underlying principles guiding the bonding in both sorts of interactions are discussed, and the trends that emerge from recent work offer a guide as to how one might design systems that allow multiple noncovalent bonds to occur simultaneously, or that prefer one bond type over another.

show abstract

Section: σ- Hole and π-Hole On The Same Atommentioning

confidence: 99%

Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons

2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…Following many decades of study of the H-bond [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ], a great deal of research has turned to closely related interactions in which the bridging proton is replaced by any of a number of larger atoms, generally drawn from the right side of the periodic table. Depending upon the specific column of the table in which these atoms lie, the noncovalent bonds are typically referred to as halogen, chalcogen, and pnicogen bonds [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. Despite the diversity of the bridging atoms, these various interactions share a number of characteristics.…”

Section: Introductionmentioning

confidence: 99%

“…On one hand, it is very strongly electron-withdrawing, so its placement on a molecule would tend to produce an intense σ-hole opposite to it [ 55 ]. Its N terminus contains a negative region along the extension of the C≡N axis, which can act as an electron donor [ 16 , 17 , 36 , 55 , 56 , 57 , 58 , 59 ]. The C atom of a C≡N-Ph can even serve as an electron donor in a halogen bond with I [ 60 ].…”

Section: Introductionmentioning

confidence: 99%

Versatility of the Cyano Group in Intermolecular Interactions

Scheiner

2020

Molecules

Self Cite

View full text Add to dashboard Cite

Several cyano groups are added to an alkane, alkene, and alkyne group so as to construct a Lewis acid molecule with a positive region of electrostatic potential in the area adjoining these substituents. Although each individual cyano group produces only a weak π-hole, when two or more such groups are properly situated, they can pool their π-holes into one much more intense positive region that is located midway between them. A NH3 base is attracted to this site, where it forms a strong noncovalent bond to the Lewis acid, amounting to as much as 13.6 kcal/mol. The precise nature of the bonding varies a bit from one complex to the next but typically contains a tetrel bond to the C atoms of the cyano groups or the C atoms of the linkage connecting the C≡N substituents. The placement of the cyano groups on a cyclic system like cyclopropane or cyclobutane has a mild weakening effect upon the binding. Although F is comparable to C≡N in terms of electron-withdrawing power, the replacement of cyano by F substituents substantially weakens the binding with NH3.

show abstract

“…Very recent calculations have noted that negative cooperative effect exists in the pnicogen bonded trimers formed by ZF 3 (Z = P, As, Sb, Bi) and a number of nucleophiles. [ 28 ] However, to our knowledge, little focus has been given to how might the π‐hole pnicogen bond be effected by the other intermolecular interaction through cooperative effect. Herein, we focus on two typical intermolecular interactions, σ‐hole halogen [ 29 ] and π‐hole triel bonding interactions, [ 30 ] wherein the group VII and III atoms act as the Lewis acid center.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on how to tune the π‐hole pnicogen bonds by substitution and cooperative effects

Zhang

2020

Int J of Quantum Chemistry

View full text Add to dashboard Cite

A systemic investigation of the substitution and cooperative effects on the P…N π‐hole pnicogen bond were performed via theoretical calculations. The structural and energetic properties of the binary complexes between a series of substituted benzonitrile and PO2F have been examined to study the substitution effect. The stability of the binary complexes increases in the order of CN < Br ≈ Cl < F < H < CH3 < NH2, in which all halogen atoms serve as the electron‐withdrawing substituents. The cooperativity between halogen/triel bond with pnicogen bond were also studied in X…NC‐Ph‐CN…PO2F and Y…Br‐Ph‐CN…PO2F complexes with X = F2, Cl2, Br2, FCl, FBr, BrCl, FCN, ClCN, BrCN, BH3, BF3, and Y = NH3, NH2CH3, NHCH2, HCN. It is found that the mutual effect of the interactions is weakened through the phenyl ring relative to the heterocyclic ring. The molecular electrostatic potential, atoms in molecules and natural bond orbital analysis were carried out to unveil the nature of these interactions. Several linear relationships have been established between the geometric parameters and the interaction energies or some electronic properties of the complexes. The distinct differences for the complexes involving BH3 and their BF3 analogs may be attributed to the greater π electron density on the BF3 moiety, and the underlying reasons are discussed in detail.

show abstract

How Many Pnicogen Bonds can be Formed to a Central Atom Simultaneously?

Cited by 30 publications

References 94 publications

Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons

Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons

Versatility of the Cyano Group in Intermolecular Interactions

Theoretical studies on how to tune the π‐hole pnicogen bonds by substitution and cooperative effects

Contact Info

Product

Resources

About