Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes
Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes
复制标题
10-14族异双金属配合物的膦配体结合和催化活性
DOI：
10.1021/acs.inorgchem.2c00229
复制
发表时间：
2022
影响因子：
4.6
通讯作者：
Vela, Javier
中科院分区：
文献类型：
--
作者：
Daniels, Carena L.;Gi, Eunbyeol;Atterberry, Benjamin A.;Blome-Fernández, Rafael;Rossini, Aaron J.;Vela, Javier
杂环化合物由于其广泛的结构和反应活性以及独特的催化能力而引起了人们的广泛兴趣。此外，这些复合物可以用作合成二元金属间化合物的单源前体。一个实例是第10族金属（Pd和Pt）的双（吡啶-2-硫醇基）二氯锗和锡络合物家族。通过取代第14族元素和与过渡金属结合的中性配体，这些杂环配合物的反应性是高度可调的。在这里，我们研究了三种不同的磷基配体，PR 3（R = Bu，Ph，和OPh）的结合能的密度泛函理论和限制性Hartree-Fock方法。PR 3配体结合能的变化趋势为PBu 3> PPh 3> P（OPh）3，与它们的σ键能力一致。这些结果证实了配体交换实验监测与31 P NMR光谱，其中较弱的结合PR 3配体被替换为一个更强的。此外，我们证明，杂环配合物是Negishi偶联反应中的活性催化剂，其中较强的结合PR 3配体抑制进入金属中心的活性位点。类似的策略可以应用于其他复合物，以更好地了解它们的配体结合能，并预测它们作为前体和催化剂的反应性。
Heterobimetallic complexes have attracted much interest due to their broad range of structures and reactivities as well as unique catalytic abilities. Additionally, these complexes can be utilized as single-source precursors for the synthesis of binary intermetallic compounds. An example is the family of bis(pyridine-2-thiolato)dichloro-germanium and tin complexes of group 10 metals (Pd and Pt). The reactivity of these heterobimetallic complexes is highly tunable through substitution of the group 14 element and the neutral ligand bound to the transition metal. Here, we study the binding energies of three different phosphorous-based ligands, PR3(R = Bu, Ph, and OPh) by density functional theory and restricted Hartree–Fock methods. The PR3ligand-binding energies follow the trend of PBu3> PPh3> P(OPh)3, in agreement with their sigma-bonding ability. These results are confirmed by ligand exchange experiments monitored with31P NMR spectroscopy, in which a weaker binding PR3ligand is replaced with a stronger one. Furthermore, we demonstrate that the heterobimetallic complexes are active catalysts in the Negishi coupling reaction, where stronger binding PR3ligands inhibit access to an active site at the metal center. Similar strategies could be applied to other complexes to better understand their ligand-binding energetics and predict their reactivity as both precursors and catalysts.