Hauser Adrian, Münzfeld Luca, Schlittenhardt Sören, Köppe Ralf, Uhlmann Cedric, Rauska Ulf-Christian, Ruben Mario, Roesky Peter W
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 15 D-76131 Karlsruhe Germany
Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz-Platz 1 D-76344 Eggenstein-Leopoldshafen Germany.
Chem Sci. 2023 Feb 3;14(8):2149-2158. doi: 10.1039/d2sc06730g. eCollection 2023 Feb 22.
Synthesis of new organo-lanthanide polyphosphides with an aromatic -[P] moiety and a -[P] moiety is presented. For this purpose, the divalent Ln-complexes [(NON)Ln(thf)] (Ln = Sm, Yb) ((NON) = 4,5-bis(2,6-diisopropylphenyl-amino)-2,7-di--butyl-9,9-dimethylxanthene) and trivalent Ln-complexes [(NON)LnBH(thf)] (Ln = Y, Sm, Dy) were used as precursors in the reduction process of white phosphorus. While using [(NON)Ln(thf)] as a one-electron reducing agent the formation of organo-lanthanide polyphosphides with a -[P] Zintl anion was observed. For comparison, we investigated a multi-electron reduction of P by a one-pot reaction of [(NON)LnBH(thf)] with elemental potassium. As products molecular polyphosphides with a -[P] moiety were isolated. The same compound could also be obtained by reducing the -[P] Zintl anion within the coordination sphere of Sm in [{(NON)Sm(thf)}(μ-η:η-P)]. Reduction of a polyphosphide within the coordination sphere of a lanthanide complex is unprecedented. Additionally, the magnetic properties of the dinuclear Dy-compound bearing a bridging -[P] moiety were investigated.
本文介绍了具有芳基-[P]部分和-[P]部分的新型有机镧系多磷化物的合成。为此，在白磷还原过程中，二价镧系配合物[(NON)Ln(thf)]（Ln = Sm，Yb）（(NON) = 4,5-双(2,6-二异丙基苯基氨基)-2,7-二叔丁基-9,9-二甲基呫吨）和三价镧系配合物[(NON)LnBH(thf)]（Ln = Y，Sm，Dy）被用作前体。当使用[(NON)Ln(thf)]作为单电子还原剂时，观察到带有-[P]锌试剂阴离子的有机镧系多磷化物的形成。为了进行比较，我们研究了[(NON)LnBH(thf)]与元素钾的一锅反应对P的多电子还原。作为产物，分离出了带有-[P]部分的分子多磷化物。同样的化合物也可以通过在[{(NON)Sm(thf)}(μ-η:η-P)]中Sm的配位球内还原-[P]锌试剂阴离子来获得。镧系配合物配位球内多磷化物的还原是前所未有的。此外，还研究了带有桥连-[P]部分的双核Dy化合物的磁性。
