Geometry at the aliphatic tertiary carbon atom: computational and experimental test of the Walsh rule

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F04%3A00011337" target="_blank" >RIV/60461373:22310/04:00011337 - isvavai.cz</a>

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Geometry at the aliphatic tertiary carbon atom: computational and experimental test of the Walsh rule

Original language description

The geometrical parameters of molecules of 2-substituted 2-methylpropanes and 1-substituted bicyclo[2.2.2]octanes were calculated at the B3LYP/6-311+G(d,p) level. They agreed reasonably well with the mean crystallographic values retrieved from the Cambridge Structural Database for a set of diverse non-cyclic structures with a tertiary C atom. The angle deformations at this C atom produced by the immediately bonded substituent are also closely related to those observed previously in benzene mono derivatives (either as calculated or as derived from crystallographic data). The calculated geometrical parameters were used to test the classical Walsh rule: It is evidently true that an electron-attracting substituent increases the proportion of C-atom p-electrons in the bond to the substituent and leaves more s-electrons to the remaining bonds; as a consequence the C-C-C angles at a tertiary carbon are widened and the C-C bonds shortened. However, this rule describes only part of the reality

Czech name

Geometrie na alifatickém terciárním atomu uhlíku: výpočetní a experimentální test Walshova pravidla

Czech description

Geometrie na alifatickém terciárním atomu uhlíku: výpočetní a experimentální test Walshova pravidla

Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CH - Nuclear and quantum chemistry, photo chemistry

OECD FORD branch

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Project

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Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2004

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Acta Crystallogr.

ISSN

0365-110X

e-ISSN

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Volume of the periodical

B60

Issue of the periodical within the volume

1

Country of publishing house

DE - GERMANY

Number of pages

5

Pages from-to

103-107

UT code for WoS article

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EID of the result in the Scopus database

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