Phosphine Ligands in the Palladium-Catalysed Methoxycarbonylation of Ethene: Insights into the Catalytic Cycle through an HP NMR Spectroscopic Study
作者:Verónica de la Fuente、Mark Waugh、Graham R. Eastham、Jonathan A. Iggo、Sergio Castillón、Carmen Claver
DOI:10.1002/chem.200903158
日期:——
backbone, ligands 7 and 9, containing four‐ and six‐membered ring backbones giving more active systems. The acid used as co‐catalyst has a strong influence on the activity, with excess trifluoroacetic acid affording the highest conversion, whereas excess methyl sulfonic acid inhibits the catalytic system. An in operando NMR spectroscopic mechanistic study has established the catalytic cycle and resting
新颖顺-1,2-双(二-叔丁基膦)碳配位体6 - 9已经制备和相应的钯络合物[钯(O 3 SCH 3)(L-L)] [0 3 SCH 3 ] (L- L =二膦)32 - 35合成并表征了通过NMR光谱法和X射线衍射。这些二膦配体为钯催化的乙烯的甲氧羰基化提供了非常活泼的催化剂。活性随碳环骨架,配体7和9的大小而变化,其中包含四元和六元环主干,从而提供了更活跃的系统。用作助催化剂的酸对活性有很大影响,过量的三氟乙酸可提供最高的转化率,而过量的甲基磺酸会抑制催化体系。进行中的NMR光谱机理研究已经确定了在操作反应条件下催化剂的催化循环和静止状态。尽管催化作用遵循氢化物途径,但静止状态显示为氢化物前体络合物[Pd(O 3 SCH 3)(L- L)] [O 3 SCH 3 ],这表明可分离/检测到的氢化物络合物是不是此机制的先决条件。