Correlation between Hammett substituent constants and directly calculated π-conjugation strength

被引：92

作者：

Fernández, I ^{[1
]}

Frenking, G ^{[1
]}

机构：

[1] Univ Marburg, Fachbereich Chem, D-35043 Marburg, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2006年 / 71卷 / 06期

关键词：

D O I：

10.1021/jo052012e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] The results of an energy decomposition analysis of ortho-, meta-, and para-substituted benzylic cations and para-substituted benzylic anions H2C-C6H4Rq (R = H, F, CN, Me, OH, NH2, NO2, CHO, CO2H; q = +, -) are presented and discussed. The calculated values for the pi bonding between CH2q and C6H4R show for substituents which have pi orbitals a linear correlation with the Hammett sigma(p), sigma(+)(p), and sigma(m) constants.

引用

页码：2251 / 2256

页数：6

共 37 条

[1] An experimental and theoretical study of the substituent effects on the redox properties of 2-[(R-phenyl)amine]-1,4-naphthalenediones in acetonitrile [J].

Aguilar-Martínez, M ;

Cuevas, G ;

Jiménez-Estrada, M ;

González, I ;

Lotina-Hennsen, B ;

Macías-Ruvalcaba, N .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (10) :3684-3694

[2] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[3] Kohn-Sham density functional theory: Predicting and understanding chemistry [J].

Bickelhaupt, FM ;

Baerends, EJ .

REVIEWS IN COMPUTATIONAL CHEMISTRY, VOL 15, 2000, 15 :1-86

[4]

Brownlee R. T. C., 1973, PROGR PHYS ORG CHEM, V10, P1, DOI DOI 10.1002/9780470171899.CH1

[5] Direct estimate of the conjugative and hyperconjugative stabilization in diynes, dienes, and related compounds [J].

Cappel, D ;

Tüllmann, S ;

Krapp, A ;

Frenking, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (23) :3617-3620

[6]

Carey F.A., 2000, ADV ORGANIC CHEM A, V3

[7]

Charton M., 1987, PROG PHYS ORG CHEM, V16, P287

[8]

Charton M., 1981, PROG PHYS ORG CHEM, P119, DOI DOI 10.1002/9780470171929.CH3

[9] The nature of the chemical bond revisited.: An energy partitioning analysis of diatomic molecules E2 (E=N-Bi, F-I), CO and BF [J].

Esterhuysen, C ;

Frenking, G .

THEORETICAL CHEMISTRY ACCOUNTS, 2004, 111 (2-6) :381-389

[10] Towards a rigorously defined quantum chemical analysis of the chemical bond in donor-acceptor complexes [J].

Frenking, G ;

Wichmann, K ;

Fröhlich, N ;

Loschen, C ;

Lein, M ;

Frunzke, J ;

Rayón, VM .

COORDINATION CHEMISTRY REVIEWS, 2003, 238 :55-82

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