Tetrel Bonding along the Pathways of Transsilylation and Alkylation of<i>N</i>-Trimethylsilyl-<i>N</i>-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

Chípanina, N. N.; Lazareva, N. F.; Oznobikhina, Larisa P.; Shainyan, B. А.

doi:10.1021/acs.jpca.9b03876

Cited by 5 publications

(1 citation statement)

References 74 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, tetrel bonding has received much attention due to its stabilizing role in S N 2 reactions. 23 A survey of the recent literature reveals there are a number of theoretical and experimental works describing the ability of the lighter tetrels carbon 24,25 and silicon 26,27 to act as electrophilic sites, whereas experimental investigations of the heavier group 14 elements such as tin, germanium, and lead are relatively limited and less systematic. 28 We note the recent work of Baker and co-workers which describes the construction of supramolecular assemblies via the rational utilization of Sn•••O tetrel bonds involving a series of tin complexes of the Schiff's base salicylaldehyde acyldihydrazone with a methylene spacer.…”

Section: ■ Introductionmentioning

confidence: 99%

Short and Linear Intermolecular Tetrel Bonds to Tin. Cocrystal Engineering with Triphenyltin Chloride

Kumar

Rodrigue

Bryce

2020

Crystal Growth & Design

View full text Add to dashboard Cite

Group 14 (tetrel) elements potentially provide a region of low electronic density (σ-hole) and elevated electrostatic potential, which acts as an electrophilic site to form attractive interactions with electron-rich moieties. Tetrel bonds are the result of net attractive interaction between an electrophilic region associated with a tetrel atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Here, we describe a systematic study of the potential utility of tetrel bonds to tin for engineering novel cocrystalline architectures. We report the preparation of 10 new tetrel-bonded cocrystals of triphenyltin chloride with various Lewis bases featuring oxygen and nitrogen electron donor atoms. Single-crystal X-ray diffraction studies reveal that the formation of short and directional Sn···O and Sn···N tetrel bonds along the extension of the Cl–Sn covalent bond is chiefly responsible for the self-assembly of the two complementary components. Normalized contact parameters of approximately 0.6, tetrel bond angles of approximately 170–180°, and lengthening of the covalent Sn–Cl bond by 6–9% upon cocrystallization are all characteristic of the observed tetrel bonds to tin. Substantial changes in the isotropic 119Sn chemical shifts suggest the persistence of the tin tetrel bond in solution.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Short and Linear Intermolecular Tetrel Bonds to Tin. Cocrystal Engineering with Triphenyltin Chloride

Kumar

Rodrigue

Bryce

2020

Crystal Growth & Design

View full text Add to dashboard Cite

show abstract

Noncovalent Bonds between Tetrel Atoms

et al. 2020

View full text Add to dashboard Cite

The pairing of TFH3 with a TH2CH3− anion, where T represents tetrel atoms C, Si, Ge, Sn, Pb, results in a strong direct interaction between the two T atoms. The interaction energy is sensitive to the nature of the two T atoms but can be as large as 90 kcal/mol. The noncovalent bond strength rises quickly as the basic T atom of the anion becomes smaller, or as the Lewis acid T grows larger, although there is less sensitivity to the latter atom. The electrostatic component makes up some 55–70 % of the total attraction energy. This term is well accounted for by simple combination of the maximum and minimum values of the molecular electrostatic potential of the Lewis acid and base units, respectively. The complexation induces a rearrangement in the TFH3 molecule from tetrahedral to trigonal pyramidal. The associated deformation energy reduces the exothermicity of the complexation reaction. Electron density shift patterns reveal a density loss on the basic T atom, along with accompanying increases on the acidic T and its attached F atom.

show abstract

The Rivalry between Intramolecular Tetrel Bonds and Intermolecular Hydrogen Bonds in (O−Si) Chelates of N‐Silylmethylamides and ‐ureas. A Theoretical Study

Chipanina,

Shainyan,

Oznobikhina

et al. 2024

ChemPhysChem

View full text Add to dashboard Cite

The comparison of the results of theoretical calculations of (O−Si) chelates of N‐silylmethylated amides and ureas with the axial chlorine or fluorine atom at silicon to the data of X‐ray analysis of related compounds revealed the formation of covalent O−Si tetrel bonds (TB) or noncovalent O⋅⋅⋅Si tetrel bonds (NTB). The nature of the formed tetrel bond depends on the substituents at silicon and the polarity of the medium. The competition between the intramolecular TB and intermolecular hydrogen bonds (HB) with proton donors depends on the center of basicity involved in the formation of HB, which could be either oxygen or halogen. The hydrogen bonding can result in changing the nature of the tetrel bonds from covalent to noncovalent and vice versa by varying their lengths and energies. The O−Si bond energies estimated by QTAIM analysis of N‐[(chlorodimethylsilyl)methyl]‐N‐methylacetamide and its H‐complexes vary within the range of 7.2 and 12 kcal/mol in gas and solution, respectively, and correlate with the O−Si bond lengths.

show abstract

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

Cited by 5 publications

References 74 publications

Short and Linear Intermolecular Tetrel Bonds to Tin. Cocrystal Engineering with Triphenyltin Chloride

Short and Linear Intermolecular Tetrel Bonds to Tin. Cocrystal Engineering with Triphenyltin Chloride

Noncovalent Bonds between Tetrel Atoms

The Rivalry between Intramolecular Tetrel Bonds and Intermolecular Hydrogen Bonds in (O−Si) Chelates of N‐Silylmethylamides and ‐ureas. A Theoretical Study

Contact Info

Product

Resources

About