ELECTRONIC-STRUCTURE AND PHOTOCHEMICAL INTERCONVERSIONS OF DIHYDROPENTALENE RADICAL CATIONS

被引：6

作者：

BALLY, T ^{[1
]}

TRUTTMANN, L ^{[1
]}

WANG, JT ^{[1
]}

WILLIAMS, F ^{[1
]}

机构：

[1] UNIV TENNESSEE,DEPT CHEM,KNOXVILLE,TN 37996

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1995年 / 117卷 / 30期

关键词：

D O I：

10.1021/ja00135a010

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Starting from the recently characterized radical cation of bicyclo[3.3.0]octa-2,6-diene-4,8-diyl, four additional dihydropentalene radical cations (DHP.+) can be formed by phototautomerization in Freon glasses and argon matrices where they can be characterized by optical (Freon, argon) and ESR spectroscopy (Freon), Two of these DHP isomers can be prepared independently, while the cations of the other two are identified by analogy of their spectra with those of related compounds. The electronic structure of 1,2-, 1,4-, and 1,5-DHP.+, which have linear and cross-conjugated triene pi-systems is discussed on the basis of their photoelectron and optical spectra and INDO/S calculations. The part of the C8H8.+ potential surface comprising all ten possible DHP.+ tautomers and some related valence isomers is explored by high-level ab initio calculations. An FMO-based set of rules for sigmatropic rearrangements in radical cations is presented and serves to rationalize the observed H-shifts.

引用

页码：7923 / 7934

页数：12

共 48 条

[1]

Shida T., Iwata S., J. Am. Chem, Soc., 95, (1973)

[2]

Dai S., Wang J.T., Williams F., J. Am. Chem. Soc., 112, (1990)

[3]

Dai S., Wang J.T., Williams F., J. Am. Chem. Soc., 112, (1990)

[4]

Bally T., Truttmann L., Dai S., Wang J.T., Williams. F. Chem. Phys. Lett., 212, (1993)

[5]

Bally T., Truttmann L., Dai S., Williams F., J. Am. Chem. Soc., 117, (1995)

[6]

Meier H., Pauli A., Kolshorn H., Kochhan P., Chem. Ber., 120, (1987)

[7]

Meier H., Pauli A., Kochhan P., Synthesis, (1987)

[8]

Pauli A., Kolshorn H., Meier H., Chem. Ber., 120, (1987)

[9]

Turro N.J., Liu J.-M., Zimmerman H.E., Factor R.E., J. Org. Chem., 45, (1980)

[10]

Griesbeck A., J. Org. Chem., 54, (1989)

← 1 2 3 4 5 →