Relating Bond Angles of Dihalo- and Tetrahydro--methanes, -silanes, and -germanes to Electronegativities

Kirschenbaum, Louis J.; Ruekberg, Ben

doi:10.1021/ed200355u

Cited by 4 publications

(2 citation statements)

References 19 publications

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“…Except for a few exceptions 13c,29–31 and the recent extension to transition metal compounds, the correlation of hybridization and electronegativity has not been widely useful for non‐carbon systems . We had shown recently that Bent's rule is widely applicable to main group elements and can assist in structural analysis of molecular systems throughout the periodic system …”

Section: Hybridization and Electronegativity: An Mo Model For Bent's mentioning

confidence: 99%

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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Section: Hybridization and Electronegativity: An Mo Model For Bent's mentioning

confidence: 99%

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

Alabugin

Bresch

Gomes

2014

J of Physical Organic Chem

127

119

View full text Add to dashboard Cite

show abstract

“…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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Water Entrapped inside Fullerene Cages: A Potential Probe for Evaluation of Bond Polarization

et al. 2016

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The concept of the bond polarization is a useful tool to understand chemical reactions and fundamental properties of compounds. However, experimental considerations are limited owing to its difficulty of reliable description. We demonstrated that geometrically isolated H 2 O inside the cage of fullerene C 60 is a possible probe to evaluate the polarization degree of covalent bonds C(C 60 ) À X (X = heteroatom) on the C 60 cage. The 1 H NMR relaxation times of entrapped H 2 O have been systematically measured at variable temperatures for H 2 O@C 60 X (X = CR 2 , NR, O, and O 2 ). The results followed in the order of electronegativities of C (2.55), N (3.04), and O (3.44), indicating that entrapped H 2 O can sensitively respond to the degree of the bond polarization.

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Relating Bond Angles of Dihalo- and Tetrahydro--methanes, -silanes, and -germanes to Electronegativities

Cited by 4 publications

References 19 publications

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

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

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

Water Entrapped inside Fullerene Cages: A Potential Probe for Evaluation of Bond Polarization

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