Perdriau Sébastien, Chang Mu-Chieh, Otten Edwin, Heeres Hero J, de Vries Johannes G
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands), Fax: (+31) 50-3634296.
Chemistry. 2014 Nov 17;20(47):15434-42. doi: 10.1002/chem.201403236. Epub 2014 Sep 26.
The [Ru(CO)H(PNN)] pincer complex based on a dearomatised PNN ligand (PNN: 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) was examined for its ability to isomerise alkenes. The isomerisation reaction proceeded under mild conditions after activation of the complex with alcohols. Variable-temperature (VT) NMR experiments to investigate the role of the alcohol in the mechanism lend credence to the hypothesis that the first step involves the formation of a rearomatised alkoxide complex. In this complex, the hemilabile diethylamino side-arm can dissociate, allowing alkene binding cis to the hydride, enabling insertion of the alkene into the metal-hydride bond, whereas in the parent complex only trans binding is possible. During this study, a new uncommon Ru(0) coordination complex was also characterised. The scope of the alkene isomerisation reaction was examined.
研究了基于去芳构化PNN配体（PNN：2-二叔丁基膦甲基-6-二乙氨基甲基吡啶）的[Ru(CO)H(PNN)]钳形配合物异构化烯烃的能力。在用醇类活化该配合物后，异构化反应在温和条件下进行。通过变温（VT）核磁共振实验研究醇类在该机理中的作用，这支持了第一步涉及形成再芳构化醇盐配合物的假设。在这种配合物中，半不稳定的二乙氨基侧臂可以解离，使烯烃能够与氢化物顺式配位，从而使烯烃插入金属-氢键中，而在母体配合物中只能进行反式配位。在这项研究中，还对一种新的罕见Ru(0)配位配合物进行了表征。研究了烯烃异构化反应的范围。
