To develop new hemilabile ligand systems for the green synthesis of substituted olefins via Heck cross-coupling reactions in supercritical CO₂, we designed and synthesized three palladium(II) complexes bearing heterodonor phosphine-imine ligands which were effectively used in organic solvents in terms of various Pd-catalyzed cross-coupling reactions. These newly prepared palladium(II) complexes and previously reported analogs by us were modified with perfluorooctyl (-C₈F₁₇) groups to provide their solubilization in supercritical CO₂ to be applied as homogenous catalyst. Both catalytic efficiency and selectivity were benchmarked in the Heck cross-coupling reactions, this representing the first example of the use of hemilabile phosphine-imines as ligands in supercritical CO₂ solvent. This ligand system leads to lower reaction times, good conversions and selectivities than the previously reported well-known mono- or bisphosphine palladium precatalysts. Moreover, the phosphine-imine based palladium(II) precatalysts show tolerance of a wide variety of substrates on both olefin and aryl halides.

为了开发新的半不稳定配体体系，用于通过超临界CO _2中的Heck交叉偶联反应绿色合成取代烯烃，我们设计并合成了三种带有杂多给体膦亚胺配体的钯（II）配合物，这些配合物可有效地用于有机溶剂中。各种Pd催化的交叉偶联反应。这些新制备的钯（II）配合物和我们先前报道的类似物用全氟辛基（-C ₈ F ₁₇）基团修饰，以使其可溶于超临界CO _2中。用作均相催化剂。催化效率和选择性均在Heck交叉偶联反应中进行了基准测试，这代表了使用半不稳定的膦亚胺作为超临界CO ₂溶剂中的配体的第一个例子。与先前报道的众所周知的单或双膦钯钯预催化剂相比，这种配体体系可缩短反应时间，提高转化率和选择性。此外，基于膦亚胺的钯（II）预催化剂在烯烃和芳基卤化物上均表现出对多种底物的耐受性。