School of Science and Technology, Nottingham Trent University , Nottingham NG11 8NS, United Kingdom.
Institute of Chemical Sciences, Heriot-Watt University , Edinburgh EH14 4AS, United Kingdom.
J Am Chem Soc. 2016 Jun 8;138(22):6964-7. doi: 10.1021/jacs.6b04060. Epub 2016 May 27.
The palladium(II) chlorostibine complex [PdCl2(SbMe2Cl)2]2 has a dimeric structure in the solid state, stabilized by hyper-coordination at the Lewis amphoteric Sb centers. Reaction with 8 equiv of MeLi forms [Pd4(μ3-SbMe3)4(SbMe3)4], whose structure comprises a tetrahedral Pd(0) core with four terminal SbMe3 ligands and four μ3-SbMe3 ligands, one capping each triangular Pd3 face. Density functional theory calculations, supported by energy decomposition analysis and the natural orbitals for chemical valence scheme, highlight significant donor and acceptor orbital contributions to the bonding between both the terminal and the bridging SbMe3 ligands and the Pd4 core.
二氯代二(三甲基锡)合钯(II)配合物[PdCl2(SbMe2Cl)2]2 在固态中具有二聚体结构，由路易斯两性 Sb 中心的超配位稳定。与 8 当量的 MeLi 反应生成[Pd4(μ3-SbMe3)4(SbMe3)4]，其结构包括一个四面体 Pd(0)核，四个末端 SbMe3 配体和四个μ3-SbMe3 配体，每个 SbMe3 配体分别覆盖在三角形 Pd3 面的一个角上。密度泛函理论计算，辅以能量分解分析和自然轨道化学价方案，突出了终端和桥联 SbMe3 配体与 Pd4 核之间的键合中显著的供体和受体轨道贡献。
