Rehybridization in annelated benzene and dissociating glyoxal

Ou, Ming-Chiu; Chu, San‐Yan

doi:10.1016/s0166-1280(96)05008-7

Cited by 4 publications

(2 citation statements)

References 29 publications

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“…Annelation of benzene to saturated rings leads to ring deformation with strain induced bond localization (the Mills‐Nixon effect) 26. Deformation of the benzene framework in these strained systems27 is accompanied by rehybridization,28 which we analyzed quantitatively at the B3LYP/6–31G** level in this section, using a family of benzenes fused with saturated rings ( A–G in Table5).…”

Section: Methodsmentioning

confidence: 99%

Rehybridization as a general mechanism for maximizing chemical and supramolecular bonding and a driving force for chemical reactions

Alabugin

Manoharan

2006

J Comput Chem

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Dynamic variations in hybridization patterns (rehybridization) were analyzed at B3LYP/6-31G** and MP2/6-31þG* levels. Computations clearly illustrate the generality of rehybridization in a variety of chemical phenomena, which involve structural reorganization in hydrogen-bonded complexes, nonhyperconjugative stereoelectronic effects in saturated heterocycles, Mills-Nixon effect, and contrasting substituent effects in cycloaromatization reactions.q

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Section: Methodsmentioning

confidence: 99%

Rehybridization as a general mechanism for maximizing chemical and supramolecular bonding and a driving force for chemical reactions

Alabugin

Manoharan

2006

J Comput Chem

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“…Although Bent’s rule explains a wide variety of rehybridization effects used in control of reactivity in organic compounds, − the correlation of hybridization and electronegativity has not been widely useful for noncarbon systems (except for a few notable exceptions, ,− especially the recent extension to transition metal compounds). − …”

Section: Introductionmentioning

confidence: 99%

Hybridization Trends for Main Group Elements and Expanding the Bent’s Rule Beyond Carbon: More than Electronegativity

2014

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Trends in hybridization were systematically analyzed through the combination of DFT calculations with NBO analysis for the five elements X (X = B, C, N, O, and F) in 75 HnX-YHm compounds, where Y spans the groups 13-17 of the periods 2-4. This set of substrates probes the flexibility of the hybridization at five atoms X through variations in electronegativity, polarizability, and orbital size of Y. The results illustrate the scope and limitations of the Bent's rule, the classic correlation between electronegativity and hybridization, commonly used in analyzing structural effects in carbon compounds. The rehybridization effects are larger for fluorine- and oxygen-bonds than they are in the similar bonds to carbon. For bonds with the larger elements Y of the lower periods, trends in orbital hybridization depend strongly on both electronegativity and orbital size. For charged species, the effects of substituent orbital size in the more polarizable bonds to heavier elements show a particularly strong response to the charge introduction at the central atom. In the final section, we provide an example of the interplay between hybridization effects with molecular structure and reactivity. In particular, the ability to change hybridization without changes in polarization provides an alternative way to control structure and reactivity, as illustrated by the strong correlation of strain in monosubstituted cyclopropanes with hybridization in the bond to the substituent.

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Orbital hybridization: a key electronic factor in control of structure and reactivity

Alabugin

Bresch

Gomes

2014

J of Physical Organic Chem

127

119

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This review outlines fundamental factors responsible for hybridization trends in organic and main group compounds. Hybridization is a classic chemical concept that transcends textbook organic chemistry. Hybridization effects are omnipresent, and their understanding is essential for the unraveling of many structural and reactivity puzzles. Even when they are masked by a stronger effect (e.g., allylic delocalization), they still lurk below the surface. Overriding such effects comes with a penalty, whereas incorporation into reaction design provides an efficient tool for the control of reactivity.

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Rehybridization in annelated benzene and dissociating glyoxal

Cited by 4 publications

References 29 publications

Rehybridization as a general mechanism for maximizing chemical and supramolecular bonding and a driving force for chemical reactions

Rehybridization as a general mechanism for maximizing chemical and supramolecular bonding and a driving force for chemical reactions

Hybridization Trends for Main Group Elements and Expanding the Bent’s Rule Beyond Carbon: More than Electronegativity

Orbital hybridization: a key electronic factor in control of structure and reactivity

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