DFT prediction of ground-state spin multiplicity of cyclobutane-1,3-diyls: Notable effects of two sets of through-bond interactions

被引：33

作者：

Abe, M

Ishihara, C

Nojima, M

机构：

[1] Osaka Univ, Grad Sch Engn, HANDAI FRC, Dept Chem Mat, Suita, Osaka 5650871, Japan

[2] Osaka Univ, Grad Sch Engn, HANDAI FRC, Frontier Res Ctr, Suita, Osaka 5650871, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 04期

关键词：

D O I：

10.1021/jo026345c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

DFT calculations (UB3LYP/6-31+G**) have been performed to predict the substituent effect on the ground-state spin-multiplicity and the singlet-triplet energy gap in cyclobutane-1,3-diyls, CB-DR. The ground state is calculated to be largely dependent on the substituents (X, Y) at the C2 and C4 positions. The substituent effects can be reasonably explained by the two sets of through-bond (TB) interactions which result from the coupling between the symmetric nonbonding molecular orbital (Psi(S)) and the C-X (Y) sigma and sigma* orbitals.

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页码：1618 / 1621

页数：4

相关论文

共 29 条

[1] On the electronic character of localized singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals: Substituent effects on the lifetime [J].

Abe, M ;

Adam, W ;

Hara, M ;

Hattori, M ;

Majima, T ;

Nojima, M ;

Tachibana, K ;

Tojo, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6540-6541

[2] Photochemical generation and methanol trapping of localized 1,3 and 1,4 singlet diradicals derived from a spiroepoxy-substituted cyclopentane-1,3-diyl [J].

Abe, M ;

Adam, W ;

Nau, WM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (44) :11304-11310

[3] Intramolecular and intermolecular reactivity of localized singlet diradicals: The exceedingly long-lived 2,2-diethoxy-1,3-diphenylcyclopentane-1,3-diyl [J].

Abe, M ;

Adam, W ;

Heidenfelder, T ;

Nau, WM ;

Zhang, XY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (09) :2019-2026

[4] Transient spectroscopy of a derivative of 2,2-difluoro-1,3-diphenylcyclopentane-1,3-diyl - A persistent localized singlet 1,3-diradical [J].

Adam, W ;

Borden, WT ;

Burda, C ;

Foster, H ;

Heidenfelder, T ;

Heubes, M ;

Hrovat, DA ;

Kita, F ;

Lewis, SB ;

Scheutzow, D ;

Wirz, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (03) :593-594

[5]

[Anonymous], 1982, DIRADICALS

[6] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[7] A new class of non-Kekule molecules with tunable singlet-triplet energy spacings [J].

Berson, JA .

ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (06) :238-244

[8] ELECTRON-SPIN RESONANCE STUDY OF MATRIX-ISOLATED 1,3-CYCLOPENTADIYL, A LOCALIZED 1,3-CARBON BIRADICAL [J].

BUCHWALTER, SL ;

CLOSS, GL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (13) :3857-3858

[9] GEOMETRICAL STRUCTURE AND ENERGETICS OF CLOSS DIRADICAL-1,3-CYCLOPENTADIYL [J].

CONRAD, MP ;

PITZER, RM ;

SCHAEFER, HF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (08) :2245-2246

[10] FULL VALENCE COMPLETE ACTIVE SPACE SCF, MULTIREFERENCE CI, AND DENSITY-FUNCTIONAL CALCULATIONS OF 1A1-3B1 SINGLET-TRIPLET GAPS FOR THE VALENCE-ISOELECTRONIC SERIES BH2-, CH2, NH2+, ALH2-, SIH2, PH2+, GAH2-, GEH2, AND ASH2+ [J].

CRAMER, CJ ;

DULLES, FJ ;

STORER, JW ;

WORTHINGTON, SE .

CHEMICAL PHYSICS LETTERS, 1994, 218 (5-6) :387-394