Klösener Johannes, Wiesemann Markus, Niemann Mark, Neumann Beate, Stammler Hans-Georg, Hoge Berthold
Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, 33615, Bielefeld, Germany.
Chemistry. 2018 Mar 20;24(17):4412-4422. doi: 10.1002/chem.201705770. Epub 2018 Feb 23.
In this contribution we report on the synthesis of bis(pentafluoroethyl)stannane, H Sn(C F ) . In the reaction with donor molecules a ready elimination of hydrogen and the formation of the corresponding donor-stabilized monomeric bis(pentafluoroethyl)stannylene, Sn(C F ) , becomes apparent. With dependence on the Lewis basicity and steric demand of the donor, varying coordination numbers are realized. Whereas the reaction with nitrogen bases like 4-(dimethylamino)pyridine (DMAP) leads to the complexation of two donor molecules, [Sn(C F ) (dmap) ], treatment with PMe or [Sn(C F ) ] furnished the corresponding neutral or anionic monoadducts, [Sn(C F ) (D)] (D=PMe , [Sn(C F ) ] ). In contrast, the utilization of sterically demanding donors, such as iPr O, as well as the thermal treatment of ether complexes, [Sn(C F ) (D) ] (D=Et O, THF), leads to the formation of oligomeric and cyclic stannylene moieties [Sn(C F ) ] . The reactivity of H Sn(C F ) and the donor-stabilized stannylenes was proven by hydrostannylation and complexation reactions with tetracarbonylnickel and bimetallic compounds. In the latter case, a donor-dependent stannylene or distannylene insertion into the metal-metal bond was observed.
在本论文中，我们报道了双（五氟乙基）锡烷H₂Sn(C₂F₅)₂的合成。在与给体分子的反应中，明显发生了氢的快速消除并形成了相应的由给体稳定的单体双（五氟乙基）亚锡烯Sn(C₂F₅)₂。根据给体的路易斯碱性和空间需求，实现了不同的配位数。与氮碱如4-（二甲氨基）吡啶（DMAP）反应会导致两个给体分子发生络合，生成[Sn(C₂F₅)₂(dmap)₂]，而用PMe₃或[Sn(C₂F₅)₂]处理则得到相应的中性或阴离子单加合物[Sn(C₂F₅)₂(D)]（D = PMe₃，[Sn(C₂F₅)₂]⁻）。相反，使用空间位阻较大的给体，如异丙醚，以及对醚配合物[Sn(C₂F₅)₂(D)₂]（D = Et₂O，THF）进行热处理，会导致形成低聚和环状亚锡烯部分[Sn(C₂F₅)]ₙ。通过与四羰基镍和双金属化合物的氢锡化反应和络合反应，证明了H₂Sn(C₂F₅)₂和由给体稳定化的亚锡烯的反应活性。在后一种情况下，观察到了给体依赖性的亚锡烯或二亚锡烯插入金属-金属键的现象。
