Competition between a Tetrel and Halogen Bond to a Common Lewis Acid

Scheiner, Steve

doi:10.1021/acs.jpca.0c10060

Cited by 16 publications

(19 citation statements)

References 88 publications

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“…A great number of experimental and theoretical investigations involving TtBs [2,20,64,65] are concentrated on the lighter elements (carbon and silicon), while those studying the heavier tetrels are scarcer [66][67][68][69]. Nevertheless, two excellent reviews are available including several X-ray crystal structures that prove the ability of Ge, Sn to establish highly directional interactions [70,71], which are key for assembling the crystal packing of many germanium and tin derivatives.…”

Section: Germanium and Tinmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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Elements from groups 14–18 and periods 3–6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4−, PF6−, ClO4−, etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ–hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bondings for group 18. In general, σ–hole interactions exhibit different features when moving along the same group (offering larger and more positive σ–holes) or the same row (presenting a different number of available σ–holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ–hole interactions, complemented with molecular electrostatic potential surfaces of model systems.

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Section: Germanium and Tinmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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“…Mutual Weakening. An earlier work 56 had shown that the formation of a TB on one end of the T−X bond tended to severely weaken, and in many cases even eliminate, the possibility of a XB to the other end of this bond. This idea was tested here for the T−Z bond between a tetrel and pnicogen atom.…”

Section: ■ Resultsmentioning

confidence: 99%

“…The earlier comparison 56 of a TB with a XB, again with both T and X atoms situated on the same covalent bond, had observed the TB to be much stronger than the XB, regardless of the nature of the T or X atoms, or what periodic table rows they were drawn from. This distinction was true even if the substituents on the T atom were changed from F to H. The only exception had been the cases with T = C, where a TB was questionable, with interaction energies on the order of only 1 kcal/mol.…”

Section: ■ Discussionmentioning

confidence: 97%

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Relative Strengths of a Pnicogen and a Tetrel Bond and Their Mutual Effects upon One Another

Scheiner

2021

J. Phys. Chem. A

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The ability of the T and Z atoms of TR3ZR2 to engage in a noncovalent interaction with NH3 is assessed by DFT calculations, where the T atom refers to C, Si, and Ge; Z = As, Sb, and P; and substituents R = H and F. In most instances, the tetrel bond (TB) is both stronger and shorter than the pnicogen bond (ZB). These two bond strengths can be equalized, or preference shifted to the ZB, if F substituents are placed on the Z and H on the T atoms. Employing C as the T atom results in a very weak TB, with the ZB clearly favored energetically. The simultaneous formation of both TB and ZB weakens both, particularly the latter, but both bonds survive intact. Geometric and spectroscopic perturbations of the subunits reflect the two types of noncovalent bonds.

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“…However, the required distortion to a planar unit so as to form such π‐holes was also much more energetically costly. The Si··NH 3 σ‐hole tetrel bond interaction energy of SiF 3 SbF 2 is 37 kcal/mol 86 and that for SiF 3 Cl is 36 kcal/mol 87 …”

Section: Summary and Discussionmentioning

confidence: 99%

Maximal occupation by bases of π‐hole bands surrounding linear molecules

Scheiner

2021

J Comput Chem

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Linear molecules such as CO2 contain a positive π‐hole ring that surrounds C on the molecule's equator. Quantum calculations examine the question as to how many bases can simultaneously bind to this ring. Linear molecules examined are TO2, where T = C, Si, Ge, Sn; bases are NCH and NH3. CO2 engages in the weakest of the tetrel bonds, and can bind up to three NCH and two NH3. Unlike σ‐hole tetrel bonds, Si forms the strongest tetrel bonds, with interaction energies as high as 43 kcal/mol with NH3. But like GeO2, SiO2 can sustain only two bases in its equatorial ring. The π‐hole ring of SnO2 can engage in up to four tetrel bonds with either NCH or NH3, even though these bonds are weaker than those with GeO2 or SiO2. As all of these complexes cast TO2 in the role of multiple electron acceptor, the resulting negative cooperativity makes each successive bond weaker than its predecessor as bases are added, as well as reducing the magnitude of the central molecule's π‐hole.

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Competition between a Tetrel and Halogen Bond to a Common Lewis Acid

Cited by 16 publications

References 88 publications

On the Importance of σ–Hole Interactions in Crystal Structures

On the Importance of σ–Hole Interactions in Crystal Structures

Relative Strengths of a Pnicogen and a Tetrel Bond and Their Mutual Effects upon One Another

Maximal occupation by bases of π‐hole bands surrounding linear molecules

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