Sun Xiaofei, Simler Thomas, Reiter Kevin, Weigend Florian, Roesky Peter W
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany.
Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany.
Chemistry. 2020 Nov 20;26(65):14888-14895. doi: 10.1002/chem.202003417. Epub 2020 Oct 5.
Divalent lanthanide complexes of Eu (1) and Yb (2) coordinated by a chelating pyridine-based bis(silylene) ligand were isolated and fully characterized. Compared to the Eu complex 1, the Yb complex 2 presents a lower thermal stability, resulting in the activation of one Si -N bond and formation of an Yb complex (3), which features a unique silylene-pyridyl-amido ligand. The different thermal stability of 1 and 2 points towards reduction-induced cleavage of one Si -N bond of the bis(silylene) ligand. Successful isolation of the corresponding redox-inert bis(silylene) Ca complex (5) was achieved at low temperature and thermal decomposition into a Ca complex (4) bearing the same silylene-pyridyl-amido ligand was identified. In this case, the thermolysis reaction proceeds through another, non-redox induced, mechanism. An alternative higher yielding route to 4 was developed through an in situ generated silylene-pyridyl-amine proligand.
分离并全面表征了由螯合吡啶基双（硅烯）配体配位的二价铕（1）和镱（2）镧系配合物。与铕配合物1相比，镱配合物2的热稳定性较低，导致一个Si-N键活化并形成具有独特硅烯-吡啶基-酰胺配体的镱配合物（3）。1和2不同的热稳定性表明双（硅烯）配体的一个Si-N键发生了还原诱导断裂。在低温下成功分离出相应的氧化还原惰性双（硅烯）钙配合物（5），并确定其热分解为带有相同硅烯-吡啶基-酰胺配体的钙配合物（4）。在这种情况下，热解反应通过另一种非氧化还原诱导机制进行。通过原位生成的硅烯-吡啶基-胺前体配体开发了一条通往4的替代高产率路线。
