Theoretical study of the geometrical, energetic and NMR properties of atranes

Marín‐Luna, Marta; Alkorta, Ibón; Elguero, José

doi:10.1016/j.jorganchem.2015.07.013

Cited by 31 publications

(21 citation statements)

References 74 publications

(38 reference statements)

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“…Tetrel bonds can appear within the intramolecular context of a single molecule [44][45][46][47] as in 1-methylsilatrane 48 or trifluorosilylhydrazines 44 . The concept has been broadened to include a variety of Lewis bases 49 , such as radicals [50][51] , anions 43,[52][53] , carbenes [54][55] , or π-systems [56][57][58] .…”

Section: Introductionmentioning

confidence: 99%

Steric Crowding in Tetrel Bonds

Scheiner

2018

J. Phys. Chem. A

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The tetravalent character of tetrel atoms leaves only limited room for an incoming nucleophile to approach and engage in a noncovalent bond with a tetrel atom. Any such approach can only occur at the expense of internal geometric distortions. The balance between attractive forces and repulsive steric crowding was studied for a series of Lewis acids of the type FTR (T = Si, Ge, Sn, Pb) which were allowed to interact with various bases. The strength and other properties of the tetrel bond are examined as the R groups are made progressively larger, varying from H and CH to isopropyl and tert-butyl, which induce steric crowding with the incoming base. The effects of crowding which impede the bond can be offset by enlarging the T atom, by adding electron-withdrawing substituents to the Lewis acid, or by considering stronger bases such as anions. The tetrel bond energies reach up to 10 kcal/mol for a pair of neutral molecules with no electron-withdrawing substituents on the Lewis acid. Adding -CF substituents grows the interaction energy to as high as 35 kcal/mol, and a further increment occurs for an anionic base, taking the maximum up to 54 kcal/mol.

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Section: Introductionmentioning

confidence: 99%

Steric Crowding in Tetrel Bonds

Scheiner

2018

J. Phys. Chem. A

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“…Such a skeleton of silatranes with hypervalent (pentacoordinated) silicon predetermines their unusual physical and chemical properties, for example, a strong dipole moment of the molecule, a strong electron-donor effect of the silatrane group, and, hence, a high reactivity [ 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. In contrast to the starting alkoxysilanes, a striking feature of silatranes is their relative resistance to hydrolysis ( Scheme 2 ) [ 20 , 21 , 22 , 23 ].…”

Section: Introductionmentioning

confidence: 99%

3-Aminopropylsilatrane and Its Derivatives: A Variety of Applications

et al. 2022

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Silatranes arouse much research interest owing to their unique structure, unusual physical–chemical properties, and diverse biological activity. The application of some silatranes and their analogues has been discussed in several works. Meanwhile, a comprehensive review of the wide practical usage of silatranes is still absent in the literature. The ability of silatranes to mildly control hydrolysis allows them to form extremely stable and smooth siloxane monolayers almost on any surface. The high physiological activity of silatranes makes them prospective drug candidates. In the present review, based on the results of numerous previous studies, using the commercially available 3-aminopropylsilatrane and its hybrid derivatives, we have demonstrated the high potential of 1-organylsilatranes in various fields, including chemistry, biology, pharmaceuticals, medicine, agriculture, and industry. For example, these compounds can be employed as plant growth biostimulants, drugs, optical, catalytic, sorption, and special polymeric materials, as well as modern high-tech devices.

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“…Atranes, ocanes and hypoatranes contain an intramolecular coordination bond nitrogen→element. Theoretical studies on the structure and hypervalent intramolecular coordination N→X (X = C, Si, Ge, B, P) in some atrane systems were carried out in [ 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ]; information on the structure of some ocanes is given in [ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ], and hypoatranes in [ 36 , 40 , 41 , 42 , 43 ].…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study

2020

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The mechanism of reactions of silatranes and germatranes, and their bicyclic and monocyclic analogues with one molecule of methanol or ethanol, was studied at the Density Functional Theory (DFT) B3PW91/6-311++G(df,p) level of theory. Reactions of 1-substituted sil(germ)atranes, 2,2-disubstituted sil(germ)ocanes, and 1,1,1-trisubstituted hyposil(germ)atranes with alcohol (methanol, ethanol) proceed in one step through four-center transition states followed by the opening of a silicon or germanium skeleton and the formation of products. According to quantum chemical calculations, the activation energies and Gibbs energies of activation of reactions with methanol and ethanol are close, their values decrease in the series of atranes–ocanes–hypoatranes for interactions with both methanol and ethanol. The reactions of germanium-containing derivatives are characterized by lower activation energies in comparison with the reactions of corresponding silicon-containing compounds. The annular configurations of the product molecules with electronegative substituents are stabilized by the transannular N→X (X = Si, Ge) bond and different intramolecular hydrogen contacts with the participation of heteroatoms of substituents at the silicon or germanium.

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Theoretical study of the geometrical, energetic and NMR properties of atranes

Cited by 31 publications

References 74 publications

Steric Crowding in Tetrel Bonds

Steric Crowding in Tetrel Bonds

3-Aminopropylsilatrane and Its Derivatives: A Variety of Applications

Mechanism of Reactions of 1-Substituted Silatranes and Germatranes, 2,2-Disubstituted Silocanes and Germocanes, 1,1,1-Trisubstituted Hyposilatranes and Hypogermatranes with Alcohols (Methanol, Ethanol): DFT Study

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