Structural dependence on the stereoselective formation of inverted housane in the viscosity-controlled photodenitrogenation of DBH-type azoalkanes

被引：5

作者：

Adam, W ^{[1
]}

Diedering, M

Sajimon, MC

Trofimov, AV

机构：

[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany

[2] Russian Acad Sci, Inst Biochem Phys, Moscow 119991, Russia

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2003年 / 5卷 / 02期

关键词：

D O I：

10.1039/b209182h

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The influence of structural changes on the a parameter, which represents the effective volume involved in molecular reorganizations, has been determined through the viscosity dependence of the stereoselectivity in the photodenitrogenation of the DBH-type azoalkanes 1a-c. The structural variation reveals that the stereoselective formation of housane is not only subject to the frictional impositions exerted by the solvent molecules on the flap motion of the methylene bridge, but also on the displacement of the bridgehead substituents during the inversion process.

引用

页码：329 / 332

页数：4

共 27 条

[1] THE VISCOSITY DEPENDENCE AND REACTION COORDINATE FOR ISOMERIZATION OF CIS-STILBENE [J].

ABRASH, S ;

REPINEC, S ;

HOCHSTRASSER, RM .

JOURNAL OF CHEMICAL PHYSICS, 1990, 93 (02) :1041-1053

[2] Viscosity-controlled stereoselective inversion in the photochemical denitrogenation of a stereolabeled diazabicyclo[2.2.1]heptene (DBH)-type azoalkane [J].

Adam, W ;

Martí, V ;

Sahin, C ;

Trofimov, AV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (20) :5002-5003

[3] Stereochemical memory in the temperature-dependent photodenitrogenation of bridgehead-substituted DBH-type azoalkanes:: Inhibition of inverted-housane formation in the diazenyl diradical through the mass effect (inertia) and steric hindrance [J].

Adam, W ;

García, H ;

Diedering, M ;

Martí, V ;

Olivucci, M ;

Palomares, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) :12192-12199

[4] Solvent effects in the photodenitrogenation of the azoalkane diazabicyclo [2.2.1] hept-2-ene: viscosity- and polarity-controlled stereoselectivity in housane formation from the diazenyl diradical [J].

Adam, W ;

Diedering, M ;

Trofimov, AV .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2002, 4 (06) :1036-1039

[5] Photochemical versus thermal skeletal inversion: Viscosity-controlled photodenitrogenation of a bridgehead-substituted DBH-type azoalkane and thermal syn-to-anti housane isomerization [J].

Adam, W ;

Diedering, M ;

Trofimov, AV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (19) :5427-5430

[6] Stereoselective formation of inverted housane in the denitrogenation of the diazenyl diradical photolytically derived from a stereolabeled diazabicyclo[2,2,1]hept-2-ene with bridgehead substituents as a function of solvent- and temperature-varied viscosity [J].

Adam, W ;

Martí, V ;

Sahin, C ;

Trofimov, AV .

CHEMICAL PHYSICS LETTERS, 2001, 340 (1-2) :26-32

[7] Temperature and viscosity dependence in the stereoselective formation of the inverted housane for the photochemical nitrogen loss from the deuterium-stereolabeled parent diazabicyclo[2.2.1]hept-2-ene [J].

Adam, W ;

Grüne, M ;

Diedering, M ;

Trofimov, AV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (29) :7109-7112

[8] COMPARATIVE-STUDY OF THE PYROLYSIS, PHOTOINDUCED ELECTRON-TRANSFER (PET), AND LASER-JET AND 185-NM PHOTOCHEMISTRY OF ALKYL-SUBSTITUTED BICYCLIC AZOALKANES [J].

ADAM, W ;

DENNINGER, U ;

FINZEL, R ;

KITA, F ;

PLATSCH, H ;

WALTER, H ;

ZANG, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5027-5035

[9] PHOTOCHEMISTRY OF THE AZOALKANES 2,3-DIAZABICYCLO[2.2.1]HEPT-2-ENE AND SPIRO[CYCLOPROPANE-1,7'-[2,3]DIAZABICYCLO[2.2.1]HEPT-2-ENE] - ON THE QUESTIONS OF ONE-BOND VS 2-BOND CLEAVAGE DURING THE DENITROGENATION, CYCLIZATION VS REARRANGEMENT OF THE 1,3-DIRADICALS, AND DOUBLE INVERSION [J].

ADAM, W ;

OPPENLANDER, T ;

ZANG, G .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (18) :3303-3312

[10] THE EFFECT OF FREQUENCY-DEPENDENT FRICTION ON ISOMERIZATION DYNAMICS IN SOLUTION [J].

BAGCHI, B ;

OXTOBY, DW .

JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (05) :2735-2741

← 1 2 3 →