STUDIES ON RADICAL CATIONS .3. TYPE-C VALENCE-ISOMERIC SYSTEM QUADRICYCLANE RADICAL CATION-NORBORNADIENE RADICAL CATION

被引：90

作者：

HASELBACH, E ^{[1
]}

BALLY, T ^{[1
]}

LANYIOVA, Z ^{[1
]}

BAERTSCHI, P ^{[1
]}

机构：

[1] EIDG INST REAKTORFORSCH,CH-5404 WURENLINGEN,SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1979年 / 62卷 / 02期

关键词：

D O I：

10.1002/hlca.19790620226

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The previously discussed principles involved in electrocyclic reactions of openshell ions are exemplified for a type C system, the radical cation couple quadricyclane+ (Q+)/norbornadiene+ (NBD+). Exhaustive calculations (MINDO/3) for the various states of the ions support the general predictions for such types of systems. The barrier of interconversion Q+ → NBD+ is estimated to be significantly lower than that for the corresponding neutrals. Experimental support to this prediction is obtained by γ‐irradiation of Q or NBD in an electron scavenging matrix. In both cases only NBD+ is observed, indicating that Q+ is not stable at 77 K. Previous observations and propositions referring to the system Q+/NBD+ are discussed in view of the present findings. Copyright © 1979 Verlag GmbH & Co. KGaA, Weinheim

引用

页码：583 / 592

页数：10

共 51 条

[1]

ANDREWS GD, 1973, J AM CHEM SOC, V95, P5046

[2] ANODIC-OXIDATION .13. PRODUCTS FROM BICYCLO[2.2.1]HEPT-2-ENE, BICYCLO[2.2.1]HEPTA-2,5-DIENE, AND TETRACYCLO[3.2.0.02,7.04,6]HEPTANE [J].

BAGGALEY, AJ ;

BRETTLE, R ;

SUTTON, JR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (11) :1055-1059

[3]

BALLY T, UNPUBLISHED

[4] PULSE-RADIOLYSIS STUDY OF QUENCHING OF AROMATIC CARBONYL TRIPLETS BY NORBORNADIENES AND QUADRICYCLENES - MECHANISM OF INTERCONVERSION [J].

BARWISE, AJG ;

GORMAN, AA ;

LEYLAND, RL ;

SMITH, PG ;

RODGERS, MAJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (06) :1814-1820

[5] HYDROGEN ABSTRACTION FROM HYDROCARBONS BY METHYL RADICALS FROM PHOTOLYSIS OF METHYL IODIDE IN SOLID NITROGEN [J].

BASS, CD ;

PIMENTEL, GC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (18) :3754-&

[6] GROUND-STATES OF MOLECULES .27. MINDO-3 CALCULATIONS FOR CHON SPECIES [J].

BINGHAM, RC ;

DEWAR, MJS ;

LO, DH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (06) :1302-1306

[7] GROUND-STATES OF MOLECULES .28. MINDO-3 CALCULATIONS FOR COMPOUNDS CONTAINING CARBON, HYDROGEN, FLUORINE, AND CHLORINE [J].

BINGHAM, RC ;

DEWAR, MJS ;

LO, DH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (06) :1307-1311

[8] GROUND-STATES OF MOLECULES .25. MINDO-3 - IMPROVED VERSION OF MINDO SEMIEMPIRICAL SCF-MO METHOD [J].

BINGHAM, RC ;

DEWAR, MJS ;

LO, DH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (06) :1285-1293

[9]

BISCHOF P, 1969, TETRAHEDRON LETT, V46, P4025

[10] MECHANISM OF ISOMERIZATION OF BICYCLO[2.1.0]PENT-2-ENES [J].

BRAUMAN, JI ;

FARNETH, WE ;

DAMORE, MB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (15) :5043-5044

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