Effects of α-ammonium, α-phosphonium, and α-sulfonium groups on C-H bond dissociation energies

被引：22

作者：

Song, KS ^{[1
]}

Liu, L ^{[1
]}

Guo, QX ^{[1
]}

机构：

[1] Univ Sci & Technol China, Dept Chem, Hefei 230026, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 11期

关键词：

D O I：

10.1021/jo020709j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

C-H bond dissociation energies of alpha-ammonium-, alpha-phosphonium-, or alpha-sulfonium-substituted methanes and toluenes were calculated to a precision of 1-2 kcal/mol. It was found that alpha-ammonium, alpha-phosphonium, and alpha-sulfonium. groups all destabilize a methyl radical. alpha-Ammonium. also destabilizes a benzyl radical, whereas alpha-phosphonium and alpha-sulfonium either slightly stabilize or destabilize a benzyl radical depending on their alkylation state.

引用

页码：4604 / 4607

页数：4

共 22 条

[1] FROM EQUILIBRIUM ACIDITIES TO RADICAL STABILIZATION ENERGIES [J].

BORDWELL, FG ;

ZHANG, XM .

ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (09) :510-517

[2] EFFECTS ON ANIONS AND RADICALS OF ALPHA-QUATERNARY AMMONIUM SUBSTITUENTS [J].

BORDWELL, FG ;

ZHANG, X .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (25) :6078-6079

[3] HOMOLYTIC BOND-CLEAVAGE ENERGIES OF THE ACIDIC N-H BONDS IN DIMETHYL-SULFOXIDE SOLUTION AND PROPERTIES OF THE CORRESPONDING RADICALS AND RADICAL CATIONS [J].

CHENG, JP ;

ZHAO, YY .

TETRAHEDRON, 1993, 49 (24) :5267-5276

[4] Radical substituent effects of α-sulfonium groups [J].

Cheng, JP ;

Liu, B ;

Zhang, XM .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (22) :7574-7575

[5] Homolytic cleavage energies of R-H bonds centered on carbon atoms of high electronegativity:: First general observations of O-type variation on C-HBDEs and the implication for the governing factors leading to the distinct O/S patterns of radical substituent effects [J].

Cheng, JP ;

Liu, B ;

Zhao, YY ;

Wen, Z ;

Sun, YK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (41) :9987-9992

[6]

CHENG JP, 1995, CHINESE SCI BULL, V40, P1338

[7]

Cheng JP, 1997, CHEM J CHINESE U, V18, P1080

[8] A theoretical study on the homolytic dissociation energies of H-N+ bonds [J].

Cheng, YH ;

Liu, L ;

Song, KS ;

Guo, QX .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2002, (08) :1406-1411

[9]

CHERKASOV AR, 2001, RUSS CHEM REV, V70, P1, DOI DOI 10.1070/RC2001V070N01ABEH000574

[10] Homolytic bond dissociation energies associated with acyl radicals and electron demands of acyl groups [J].

Feng, Y ;

Huang, H ;

Liu, L ;

Guo, QX .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2003, 5 (04) :685-690

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