Jaoul Arnaud, Tricoire Maxime, Moutet Jules, Cordier Marie, Clavaguéra Carine, Nocton Grégory
LCM, CNRS, Ecole polytechnique, IP Paris, Route de Saclay, Palaiseau, France.
Laboratoire de Chimie Physique, CNRS-Université Paris-Sud, Université Paris-Saclay, 15 avenue Jean Perrin, 91405 Orsay Cedex, France.
Chem Sq. 2019;3:1. doi: 10.28954/2019.csq.06.001.
This article relates the synthesis and characterization of novel heterobimetallic complexes containing a low-valent lanthanide, a tetradentate redox non-innocent ligand, the 4,5,9,10-tetraazaphenanthrene, taphen ligand and transition metal fragments of PdMe and PtMe. The experimental results are supported by a theoretical study. Investigation of their reduction properties allowed the formation of isostructural original heterotrimetallic complexes containing two Cp*Yb fragments and the (taphen)MMe (M = Pd and Pt) motifs. These complexes are stable in non-coordinating solvent such as toluene but decompose in coordinating solvents such as thf. Investigation of the internal electron transfer shows that the taphen ligand behaves as a two-electrons reservoir but is capable of transferring back only one electron in thf. This reversible electron(s) transfer is rare in organolanthanide chemistry and show the potential interest of these complexes in reductive chemistry. Additionally, the trinuclear complexes feature odd X-ray crystal structures in which a deviation of symmetry is observed. The latter observation was studied in depth using quantum chemistry calculations highlighting the role of non-covalent weak interactions.
本文讲述了新型异双金属配合物的合成与表征，这些配合物包含低价镧系元素、四齿氧化还原非无辜配体、4,5,9,10 - 四氮杂菲（taphen配体）以及PdMe和PtMe的过渡金属片段。实验结果得到了理论研究的支持。对它们还原性质的研究使得形成了含有两个Cp*Yb片段和(taphen)MMe（M = Pd和Pt）基序的同结构原始异三金属配合物。这些配合物在甲苯等非配位溶剂中稳定，但在四氢呋喃等配位溶剂中分解。对内部电子转移的研究表明，taphen配体表现为双电子库，但在四氢呋喃中仅能回传一个电子。这种可逆的电子转移在有机镧系化学中很少见，并显示出这些配合物在还原化学中的潜在价值。此外，三核配合物具有奇特的X射线晶体结构，其中观察到对称性偏差。利用量子化学计算对后一观察结果进行了深入研究，突出了非共价弱相互作用的作用。
