Gas-phase study of the formation and dissociation of Fe(CO)(4)H-2: Kinetics and bond dissociation energies

被引：30

作者：

Wang, WH ^{[1
]}

Narducci, AA ^{[1
]}

House, PG ^{[1
]}

Weitz, E ^{[1
]}

机构：

[1] NORTHWESTERN UNIV,DEPT CHEM,EVANSTON,IL 60208

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1996年 / 118卷 / 36期

关键词：

D O I：

10.1021/ja960252t

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Time-resolved IR spectroscopy has been used to study the oxidative addition of H-2 to Fe(CO)(4) and its reverse reaction, the reductive elimination of H-2 from Fe(CO)(4)H-2, in the gas phase. The rate constant for oxidative addition of H-2 shows little temperature dependence, indicating that if there is an activation barrier for this process it is small (<4 kcal mol(-1)). The activation barrier for the reductive elimination of H-2 is 20.5 +/- 2.1 kcal mol(-1). From these measurements, the average of the dissociation energies for the two Fe-H bonds in Fe(CO)(4)H-2 is calculated to be 62 +/- 2 kcal mol(-1). Kinetic measurements employing D-2 indicate small kinetic isotope effects for both the oxidative addition and reductive elimination reactions.

引用

页码：8654 / 8657

页数：4

共 37 条

[1] COMPUTATIONAL STUDY OF THE TRANSITION-STATE FOR H2 ADDITION TO VASKA-TYPE COMPLEXES (TRANS-IR(L)2(CO)X) - SUBSTITUENT EFFECTS ON THE ENERGY BARRIER AND THE ORIGIN OF THE SMALL H2/D2 KINETIC ISOTOPE EFFECT [J].