The pnictogen bond: a quantitative molecular orbital picture

Santos, Lucas de Azevedo; Hamlin, Trevor A.; Ramalho, Teodorico C.; Bickelhaupt, F. Matthias

doi:10.1039/d1cp01571k

Cited by 48 publications

(64 citation statements)

References 50 publications

(29 reference statements)

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“…The intensive scrutiny of σ-hole bonds has led to a solid understanding of the fundamental phenomena from which they draw their strength. The chain of processes, beginning with the distortion of the σ(R–X) covalent bond arising from the R–X electronegativity difference, and the resulting σ-hole in the density, which in turn leads to the positive potential, have been characterized. ,,,− Also studied extensively has been the relationship between the magnitude of the σ-hole potential and the strength of the ensuing interaction with a nucleophile and how other factors enter into the equation such as charge transfer and dispersion. ,− Research has also built a body of understanding of the effects of the σ-hole bond on the intermolecular distance and perturbations within the individual monomers, both geometric and spectroscopic. − …”

Section: Introductionmentioning

confidence: 99%

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Scheiner

2021

J. Phys. Chem. A

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Accompanying the rapidly growing list of σ-hole bonds has come the acknowledgment of parallel sorts of noncovalent bonds which owe their stability in large part to a deficiency of electron density in the area above the molecular plane, known as a π-hole. The origins of these π-holes are probed for a wide series of molecules, comprising halogen, chalcogen, pnicogen, tetrel, aerogen, and spodium bonds. Much like in the case of their σ-hole counterparts, formation of the internal covalent π-bond in the Lewis acid molecule pulls density toward the bond midpoint and away from its extremities. This depletion of density above the central atom is amplified by an electron-withdrawing substituent. At the same time, the amplitude of the π*-orbital is enhanced in the region of the density-depleted π-hole, facilitating a better overlap with the nucleophile’s lone pair orbital and a stabilizing n → π* charge transfer. The presence of lone pairs on the central atom acts to attenuate the π-hole and shift its position somewhat, resulting in an overall weakening of the π-hole bond. There is a tendency for π-hole bonds to include a higher fraction of induction energy than σ-bonds with proportionately smaller electrostatic and dispersion components, but this distinction is less a product of the σ- or π-character and more a function of the overall bond strength.

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Section: Introductionmentioning

confidence: 99%

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Scheiner

2021

J. Phys. Chem. A

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“…A task group has been charged with categorizing tetrel bonding, pnictogen bonding, and other non-covalent interactions, involving the elements of Groups 14-16 of the periodic table [4]. The proposed characteristics of these bonding interactions have emerged from observations of a variety of engineered chemical systems in the crystalline, liquid and gas phases, and examining signatures arising from IR [5,6], Raman [7,8], UV/vis [9,10], and NMR [10,11] methods, and from ab initio and density functional theory calculations [12][13][14]. The characteristic features vary from system to system because they are dependent on the nature of the electron density distribution associated with the electron donor and electron acceptor fragments driving the non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%

“…The role of pnictogen bonding containing heavier members of the pnictogen family (viz. P, As, Sb and Bi) in catalysis has also been demonstrated on several occasions [35][36][37][38], and in other areas, such as anion transport and recognition chemistry [39], solution and gas-phase chemistry [40-42], computational chemistry [13], supramolecular chemistry [43], coordination chemistry [44,45], medicinal chemistry [46], crystallography [47,48] and crystal engineering [49,50], among other research fields.…”

Section: Introductionmentioning

confidence: 99%

The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Varadwaj

Marques

et al. 2022

Compounds

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The nitrogen bond in chemical systems occurs when there is evidence of a net attractive interaction between the electrophilic region associated with a covalently or coordinately bound nitrogen atom in a molecular entity and a nucleophile in another, or the same molecular entity. It is the first member of the family of pnictogen bonds formed by the first atom of the pnictogen family, Group 15, of the periodic table, and is an inter- or intra-molecular non-covalent interaction. In this featured review, we present several illustrative crystal structures deposited in the Cambridge Structure Database (CSD) and the Inorganic Crystal Structure Databases (ICSD) to demonstrate that imide nitrogen is not the only instance where nitrogen can act as an electrophilic agent. Analysis of a set of carefully chosen illustrative crystal systems shows that a covalently bound nitrogen atom in a variety of molecular entities features a σ-hole or even a π-hole, and these have the ability to sustain attractive engagements with negative sites to form inter- and/or intramolecular interactions that drive, or assist, the formation of a crystalline phase.

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“…This overview is focused on exploring the nature of the geometric modes of pnictogen bonding, manifest in some crystals and known since the latter half of the last century but explored in greater detail more recently [ 38 , 39 , 40 , 41 , 42 , 43 ], addressing only phosphorus-centered pnictogen bonding (or simply, phosphorus bonding). Phosphorus, P, the second element of the pnictogen family, Group 15 of the periodic table, has an electronegativity of 2.19 on the Pauling scale, which is appreciably smaller than that of N (3.04).…”

Section: Introductionmentioning

confidence: 99%

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

2022

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The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.

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The pnictogen bond: a quantitative molecular orbital picture

Abstract: We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn•••A- (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional...

Cited by 48 publications

References 50 publications

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

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