Klemps Christian, Payet Elina, Magna Lionel, Saussine Lucien, Le Goff Xavier F, Le Floch Pascal
Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique-CNRS, 91128 Palaiseau cedex, France.
Chemistry. 2009 Aug 17;15(33):8259-68. doi: 10.1002/chem.200900986.
Chromium(III) complexes bearing R'N(CH2PR2)2 (PCNCP) ligands have been prepared. Upon activation with methylaluminoxane, these complexes proved to be effective in the selective tri- and tetramerization of ethylene. The formation of either 1-hexene or 1-octene was found to be highly dependent on the steric bulk of the substituents R on the phosphine moieties. This observation was rationalized by using density functional theory calculations on selected steps of the metallacyclic mechanism of the ethylene oligomerization reaction.
已制备出带有R'N(CH2PR2)2（PCNCP）配体的铬（III）配合物。在用甲基铝氧烷活化后，这些配合物在乙烯的选择性三聚和四聚反应中被证明是有效的。发现1-己烯或1-辛烯的形成高度依赖于膦部分上取代基R的空间位阻。通过对乙烯齐聚反应的金属环机理的选定步骤进行密度泛函理论计算，对这一观察结果进行了合理化解释。
