Observation of kinetic tritium isotope effects by dynamic NMR. The tautomerism of porphyrin

被引：86

作者：

Braun, J ^{[1
]}

Limbach, HH ^{[1
]}

Williams, PG ^{[1
]}

Morimoto, H ^{[1
]}

Wemmer, DE ^{[1
]}

机构：

[1] LAWRENCE BERKELEY LAB,NATL TRITIUM LABELLING FACIL,BERKELEY,CA 94720

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1996年 / 118卷 / 30期

关键词：

D O I：

10.1021/ja954146n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

As the knowledge of tritium isotope effects is desirable from a theoretical standpoint, we have applied 3H NMR in order to study these effects in the case of the double-hydron tautomerism of 15 N-labeled porphyrin. In conclusion, the determination of kinetic tritium isotope effects is a powerful application of dynamic 3H NMR. In the case of the tautomerism of porphyrin, these effects support the stepwise hydron-tunneling mechanism and can serve to test multidimensional tunneling models in the future.

引用

页码：7231 / 7232

页数：2

共 25 条

[21]

SCHERER G, 1994, J AM CHEM SOC, V113, P1230

[22] KINETIC HH HD DH DD ISOTOPE EFFECTS ON NONDEGENERATE STEPWISE REVERSIBLE DOUBLE PROTON-TRANSFER REACTIONS - NMR-STUDY OF THE TAUTOMERISM OF MESO-TETRAPHENYLCHLORIN [J].

SCHLABACH, M ;

SCHERER, G ;

LIMBACH, HH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (09) :3550-3558

[23] INTRAMOLECULAR TUNNELING EXCHANGE OF THE INNER HYDROGEN-ATOMS IN FREE-BASE PORPHYRINS [J].

SMEDARCHINA, Z ;

SIEBRAND, W ;

WILDMAN, TA .

CHEMICAL PHYSICS LETTERS, 1988, 143 (04) :395-399

[24] PHENOMENOLOGICAL MANIFESTATIONS OF QUANTUM-MECHANICAL TUNNELING .3. EFFECT ON RELATIVE TRITIUM-DEUTERIUM KINETIC ISOTOPE-EFFECTS [J].

STERN, MJ ;

WESTON, RE .

JOURNAL OF CHEMICAL PHYSICS, 1974, 60 (07) :2815-2821

[25] USE OF HYDROGEN ISOTOPE EFFECTS TO IDENTIFY THE ATTACKING NUCLEOPHILE IN THE ENOLIZATION OF KETONES CATALYZED BY ACETIC ACID [J].

SWAIN, CG ;

STIVERS, EC ;

REUWER, JF ;

SCHAAD, LJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (21) :5885-5893

← 1 2 3 →