Rai Georgina, Garçon Martí, Miller Philip W, Crimmin Mark R
Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, Shepherds Bush, London W12 0BZ, U.K.
Organometallics. 2025 Mar 8;44(6):716-719. doi: 10.1021/acs.organomet.4c00506. eCollection 2025 Mar 24.
We report the synthesis and solid-state characterization of two unusual PdZn clusters formed from the partial reduction of [PdLCl] precursors (L = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a PdZnCl core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these PdZn clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.
我们报道了通过用金属锌对[PdLCl]前体（L = dcpe或dppe）进行部分还原而形成的两种不同寻常的PdZn簇合物的合成及固态表征。这些新的簇合物已通过单晶X射线衍射进行了表征，其包含一个由两个螯合膦配体封端的PdZnCl核心，其中Zn的形式氧化态为 +1.5。虽然它们具有近似四面体排列的金属离子，但计算和键合分析（NBO，AIM）表明这些物种中Zn-Zn键合有限。溶液状态下的表征表明溶解时有动态行为，通过NMR和EPR光谱观察到了抗磁性和顺磁性物种。其中一种PdZn簇合物被证明是芳基溴均偶联反应的有效前体。
