Oxidative addition of the C-S bond of thiophene to the (C5Me5)Rh(PMe3) fragment:: A theoretical study revisited
Oxidative addition of the C-S bond of thiophene to the (C5Me5)Rh(PMe3) fragment:: A theoretical study revisited
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DOI：
10.1021/om700899n
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发表时间：
2008-08-11
期刊：
影响因子：
2.8
通讯作者：
Jones, William D.
中科院分区：
文献类型：
--
作者：
Atesin, Tuelay A.;Jones, William D.
用密度泛函理论（DFT）方法研究了噻吩与[（C5 Me 5）Rh（PMe 3）]片段的C-S键活化反应，得到了两个新的异构体C-S键活化过渡态，其中噻吩分子的配位体向C5 Me 5或PMe 3倾斜.通过内禀反应坐标（IRC）计算，发现这些过渡态连接了氧化加成产物和两个异构的eta（2）-C，S配位中间体。这些后一种中间体依次连接到两个异构的eta（1）-S和eta（2）-C，C配位物种。的能量和机械的细节进行了描述。
Density functional theory (DFT) calculations on the C-S bond activation reaction of thiophene with the [(C5Me5)Rh(PMe3)] fragment have been reinvestigated, giving two new isomeric C-S bond activation transition states, in which the coordinated thiophene molecule tilts toward either the C5Me5 ligand or the PMe3 ligand. Through intrinsic reaction coordinate (IRC) calculations, these transition states were found to connect the oxidative addition product with two isomeric eta(2)-C,S coordinated intermediates. These latter intermediates in turn connected to two isomeric eta(1)-S and eta(2)-C,C coordinated species. The energetics and mechanistic details are described.