Real-time Fourier transform IR (FTIR) spectroscopy in organometallic chemistry: Mechanistic aspects of the fac to mer photoisomerization of fac-[Mn(Br)(CO)(3)(R-DAB)]

被引：24

作者：

Kleverlaan, CJ ^{[1
]}

Hartl, F ^{[1
]}

Stufkens, DJ ^{[1
]}

机构：

[1] UNIV AMSTERDAM,JH VANT HOFF RES INST,ANORGAN CHEM LAB,NL-1018 WV AMSTERDAM,NETHERLANDS

来源：

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY | 1997年 / 103卷 / 03期

关键词：

alpha-diimine complexes; kinetics; manganese carbonyls; (photo)isomerization; real-time FTIR spectroscopy;

D O I：

10.1016/S1010-6030(96)04477-2

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：

Real-time Fourier transform IR (RT/FTIR) spectroscopy was used to study the photoisomerization of fac-[Mn(Br)(CO)(3)(R-DAB)] (R-DAB, N,N'-di-R-1,4-diazabutadiene; R=Pr-i, Bu-t) to mer-[Mn(Br)(CO)(3)(R-DAB)]. The primary photoproduct [Mn(Br)(L)(CO)(2)(R-DAB)] could be detected at room temperature for L=MeCN and identified at 273 K as a cis-cis isomer for L=P(OMe)(3). RT/FTIR spectroscopy was also used to determine the thermodynamic parameters E-a, Delta H-double dagger and Delta S-double dagger of the thermal backreaction of this mer product to the parent fac isomer. For slow reactions, GC/FTIR software was used to provide a real-time screen display of the IR spectral changes. For fast reactions ( 10(-1) 1 s), the high speed collect (HSC) kinetic software was used to collect 12 spectra s(-1) at 2 cm(-1) resolution, recording one spectrum per scan.

引用

页码：231 / 237

页数：7

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