Revision of the Dual-Substituent-Parameter Treatment; Reaction Series with a Donor Reaction Centre

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F07%3A00019332" target="_blank" >RIV/60461373:22340/07:00019332 - isvavai.cz</a>

Alternative codes found

RIV/61388963:_____/07:00087621

Result on the web

—

DOI - Digital Object Identifier

—

Result language

angličtina

Original language name

Revision of the Dual-Substituent-Parameter Treatment; Reaction Series with a Donor Reaction Centre

Original language description

The dual-substituent-parameter (DSP) treatment was challenged previously as not generally valid. Just in the fundamental reaction, dissociation of 4-substituted benzoic acids and in similar reactions, DPS does not hold for acceptor substituents because the constant reaction centre is itself an acceptor. In this communication, the reverse case was examined, i.e., a reaction series with a donor reaction centre: basicity and acidity of 4-substituted anilines, and acidity of 4-substituted phenols. The reaction energies were calculated for 19 common substituents at the level B3LYP/6-311+G(d,p)//B3LYP/6-311+G(d,p); the substituents effects were also estimated separately in uncharged molecules and in the ions in terms of isodesmic reaction. DSP is valid and its resonance term is highly significant for molecules with acceptor substituents; donor substituents behave differently and cannot be described by simple resonance constants. Basicity of substituted anilines is more complex since the subs

Czech name

Revision of the Dual-Substituent-Parameter Treatment; Reaction Series with a Donor Reaction Centre

Czech description

The dual-substituent-parameter (DSP) treatment was challenged previously as not generally valid. Just in the fundamental reaction, dissociation of 4-substituted benzoic acids and in similar reactions, DPS does not hold for acceptor substituents because the constant reaction centre is itself an acceptor. In this communication, the reverse case was examined, i.e., a reaction series with a donor reaction centre: basicity and acidity of 4-substituted anilines, and acidity of 4-substituted phenols. The reaction energies were calculated for 19 common substituents at the level B3LYP/6-311+G(d,p)//B3LYP/6-311+G(d,p); the substituents effects were also estimated separately in uncharged molecules and in the ions in terms of isodesmic reaction. DSP is valid and its resonance term is highly significant for molecules with acceptor substituents; donor substituents behave differently and cannot be described by simple resonance constants. Basicity of substituted anilines is more complex since the subs

Type

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

CEP classification

CC - Organic chemistry

OECD FORD branch

—

Project

—

Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2007

Confidentiality

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

Name of the periodical

Collection of Czechoslovak Chemical Communications

ISSN

0010-0765

e-ISSN

—

Volume of the periodical

72

Issue of the periodical within the volume

8

Country of publishing house

CZ - CZECH REPUBLIC

Number of pages

19

Pages from-to

1158-1176

UT code for WoS article

—

EID of the result in the Scopus database

—