Is there a generalized anomeric effect? Analyses from energy components and information-theoretic quantities from density functional reactivity theory

Cao, Xiaofang; Liu, Shaoqian; Rong, Chunying; Tian, Laijin; Liu, Shubin

doi:10.1016/j.cplett.2017.09.017

Cited by 36 publications

(29 citation statements)

References 26 publications

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“…Similar results have been obtained for anomic effects, cis effect, and γ‐ gauche effect, though each effect was found to have its own peculiarity.…”

Section: Recent Applicationssupporting

confidence: 82%

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

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106

116

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Using simple functionals of the electron density to appreciate and quantify molecular structure and chemical reactivity properties is a recent endeavor in density functional theory (DFT) toward the development of a new chemical reactivity theory. According to the first Hohenberg–Kohn theorem in DFT, the electron density alone should be able to determine any property in the ground state. Exchange and correlation energies are such properties, so are molecular structure and chemical reactivity, and hence they all should accurately be determined by electron density functionals. Quantities such as Shannon entropy, Fisher information, Ghosh–Berkowitz–Parr entropy, information gain, Onicescu information energy, etc., from the information‐theoretic approach are simple electron density functionals, whose analytical forms are exactly known. In this article, we demonstrate their usefulness and validity to quantify regioselectivity, stereoselectivity, and other structure and reactivity properties. We will outline the current understanding of its theoretical framework at first, and then highlight recent applications to chemical problems including isomeric and conformational stability, electrophilicity and nucleophilicity, strong covalent and weak noncovalent interactions, acidity and basicity, aromaticity and antiaromaticity, and numerous other properties. The effort of employing electron density functionals to quantify chemical concepts should open up a new door for us to ultimately develop a chemical reactivity theory using the DFT language. This article is characterized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory Structure and Mechanism > Molecular Structures Molecular and Statistical Mechanics > Molecular Interactions

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“…Similar results have been obtained for anomic effects, cis effect, and γ‐ gauche effect, though each effect was found to have its own peculiarity.…”

Section: Recent Applicationssupporting

confidence: 82%

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

Self Cite

106

116

View full text Add to dashboard Cite

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“…Similar structural features are found for the sulfur species, however,t he bending out of the Si 2 O 2 ring plane of the terminal Tg roups is much strongerp ronounced ( 59.68). [49,66,[72][73][74][87][88][89][90][91][92] Ion-pairs:A sd iscussed before, ion-pair formation stabilizes all silyliumi ons mentioned here. The difference in the SiÀEb ond lengths within the ring compared to the terminal distances is beste x-plained by as trong hyperconjugative effecto ft he lone pairs localized at both tricoordinated chalcogen atoms in a p-type atomic orbital as indicated by NBO investigations.…”

Section: Structure and Bondingmentioning

confidence: 79%

“…[49] It should be noted that there are av ariety of computational studies on oxonium and sulfonium species in literature. [49,66,[72][73][74][87][88][89][90][91][92] Ion-pairs:A sd iscussed before, ion-pair formation stabilizes all silyliumi ons mentioned here. In particular,t he highly reactive T + ion in [T]CB is strongly stabilized as can be seen from the short Si-Cl distance of 2.273 (cf.…”

Section: Structure and Bondingmentioning

confidence: 79%

“…30 kcal mol À1 ). [80,[82][83][84][85][86][87] According to SLA, the total energy density functionali se xpressed as the sum of steric,e lectrostatic and quantum effects that represent independente nergy contributions: [1]. 6.5 kcal mol À1 .B esides wave function-based methods( e.g.,a si nN BO anaylsis)t os tudy the steric influence within am olecule, there are density functional theory( DFT) based methods, which are completely different in their approacha nd may even lead to qualitatively differentr esults as those found by wave function-based methods.…”

Section: Structure and Bondingmentioning

confidence: 99%

See 1 more Smart Citation

On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions

Bläsing

Labbow

Michalik

et al. 2020

Chemistry A European J

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Attempts have been made to prepares alts with the labile tris(trimethylsilyl)chalconium ions, [(Me 3 Si) 3 E] + (E = O, S), by reacting[ Me 3 Si-H-SiMe 3 ][B(C 6 F 5 ) 4 ]a nd Me 3 Si[CB] (CB À = carborate = [CHB 11 H 5 Cl 6 ] À ,[ CHB 11 Cl 11 ] À )w ith Me 3 Si-E-SiMe 3 .I nt he reaction of Me 3 Si-O-SiMe 3 with [Me 3 Si-H-SiMe 3 ] [B(C 6 F 5 ) 4 ], al igand exchange was observed in the [Me 3 Si-H-SiMe 3 ] + cation leadingt ot he surprising formation of the persilylated [(Me 3 Si) 2 (Me 2 (H)Si)O] + oxonium ion in af ormal [Me 2 (H)Si] + instead of the desired [Me 3 Si] + transferr eaction. In contrast, the expected homoleptic persilylated [(Me 3 Si) 3 S] + ion was formed and isolated as [B(C 6 F 5 ) 4 ] À and [CB] À salt, when Me 3 Si-S-SiMe 3 was treated with either [Me 3 Si-H-SiMe 3 ] [B(C 6 F 5 ) 4 ]o rM e 3 Si[CB]. However, the addition of Me 3 Si[CB] to Me 3 Si-O-SiMe 3 unexpectedly led to the release of Me 4 Si with simultaneous formation of ac yclic dioxonium dicationo ft he type [Me 3 Si-mO-SiMe 2 ] 2 [CB] 2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamicso f the [(Me 3 Si) 3 E] + and [(Me 3 Si) 2 (Me 2 (H)Si)E] + ion formation are presented as well as mechanistic investigationso nt he template-driven transformation of the [(Me 3 Si) 3 E] + ion into a cyclic dichalconium dication [Me 3 Si-mE-SiMe 2 ] 2 2 + . Scheme1.Synthesis of silylated chalconium salts with [B(C 6 F 5 ) 4 ] À as counterion (E = O, S; T= Me 3 Si, R = alkyl).

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“…This result is consistent with that reported previously for other systems. [18][19][20][21][22][23][24][25] In Figs. 3b and 3c, when the electrostatic component is fitted together with either the exchangecorrelation or steric energy, better correlations can be obtained, suggesting that effects from exchange-correlation and steric components play minor yet indispensable roles.…”

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confidence: 99%

Principle of Chirality Hierarchy in Three-Blade Propeller Systems

Liu

2021

Preprint

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There are different kinds of molecular chirality, such as zero-dimensional point chirality, onedimensional axial chirality, 2D planar chirality, and 3D chirality. When they coexist in one system, such as in helical structures of proteins and DNA, they form a chirality hierarchy.Earlier, we showed that the chirality propensity of a lower level in a hierarchy is dictated by that of a higher level and henceforth proposed the Principle of Chirality Hierarchy. In this work, we confirm the validity of this principle in the three-blade propeller molecular system. We consider different choices for the three components of a propeller and systematically investigate the dependence of the stereoisomeric energy difference on these choices. Our results show that the preference of the 0D chirality of a functional group in the propeller system is determined by the 1D chirality, and homochirality is also a remarkable feature for this system. We also unveiled that there exists positive cooperativity and electrostatic interactions play the dominant role in determining the stereoisomeric stability difference while the roles for exchange-correlation and steric effects are minor but indispensable. The establishment and confirmation of the Principle of Chirality Hierarchy from this work should find important applications in asymmetric synthesis, macromolecular assembly, and many others.

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Is there a generalized anomeric effect? Analyses from energy components and information-theoretic quantities from density functional reactivity theory

Cited by 36 publications

References 26 publications

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions

Principle of Chirality Hierarchy in Three-Blade Propeller Systems

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