Vinyl functionalized Xantphos ligand (denoted as 4v-Xantphos) was newly synthesized and successfully doped into the PPh₃ based porous organic polymers (POPs) through the solvothermal synthesis technique. After proper coordination with Rh precursor, the resultant Xantphos doped Rh/POPs-PPh₃ catalysts exhibited high activity (TOF: 300–500 h⁻¹), chemoselectivity (87–91%) and regioselectivity (about 90:10) in the hydroformylation of long-chain olefins (C6-C12). As a representative substrate, hydroformylation of 1-octene could be easily realized in a fixed bed reactor for more than 400 h with high efficiency employing Xantphos doped Rh/POPs-PPh₃ catalyst, which represented a rare successful example that realized heterogenization of homogeneous hydrofromylation catalysts as well as the regioselectivity-control at the same time without leaching of rhodium. Interestingly, the hydroformylation reaction data indicated that the Rh species tend to coordinate with the exposed P atom from Xantphos rather than that from PPh₃ ligand in the Xantphos doped catalyst frame. More importantly, the HAADF-STEM and EXAFS characterizations indicated that Rh species demonstrated as single site dispersion in Xantphos doped Rh/POPs-PPh₃ catalyst, thus endowed the catalyst with high activity. Detailed DFT calculations revealed that the unique location of single site dispersed Rh species (Rh species coordinated with both of Xantphos and PPh₃ in the catalyst frame simultaneously) was responsible for the high linear regioselectivity and stability of the catalysts, the roles of Xantphos and PPh₃ were further elucidated in details.

新合成了乙烯基官能化的Xantphos配体（称为4v-Xantphos），并通过溶剂热合成技术成功地掺入了基于PPh ₃的多孔有机聚合物（POPs）中。在与Rh前体进行适当配位后，所得的Xantphos掺杂Rh / POPs-PPh ₃催化剂在加氢甲酰化反应中显示出高活性（TOF：300–500 h ^-1），化学选择性（87–91％）和区域选择性（大约90:10）。长链烯烃（C6-C12）的合成。作为代表性的底物，使用Xantphos掺杂的Rh / POPs-PPh ₃可以在固定床反应器中轻松实现1-辛烯的加氢甲酰化超过400小时，并且效率很高。催化剂，这是一个罕见的成功实例，可以在不浸出铑的情况下同时实现均相加氢烷基化催化剂的异质化和区域选择性控制。有趣的是，加氢甲酰化反应数据表明，Rh物种倾向于与Xantphos暴露的P原子配位，而不是在Xantphos掺杂的催化剂骨架中与PPh ₃配体暴露的P原子配位。更重要的是，HAADF-STEM和EXAFS的表征表明Rh物种表现为在Xantphos掺杂的Rh / POPs-PPh ₃催化剂中的单中心分散，因此赋予了该催化剂高活性。DFT的详细计算表明，单个位点分散的Rh物种（Rh物种与Xantphos和PPh协同作用）的独特位置同时在催化剂框架中的_3）导致了催化剂的高线性区域选择性和稳定性，进一步详细阐明了Xantphos和PPh ₃的作用。