Eberhard Karls Universität Tübingen, Institut für Anorganische Chemie, Auf der Morgenstelle 18, 72076 Tübingen (Germany).
Angew Chem Int Ed Engl. 2015 Mar 23;54(13):4087-91. doi: 10.1002/anie.201411025. Epub 2015 Feb 5.
NHC adducts of the stannylene Trip2 Sn (Trip=2,4,6-triisopropylphenyl) were reacted with zero-valent Ni, Pd, and Pt precursor complexes to cleanly yield the respective metal complexes featuring a three-membered ring moiety Sn-Sn-M along with carbene transfer onto the metal and complete substitution of the starting ligands. Thus the easily accessible NHC adducts to stannylenes are shown to be valuable precursors for transition-metal complexes with an unexpected SnSn bond. The complexes have been studied by X-ray diffraction and NMR spectroscopy as well as DFT calculations. The compounds featuring the structural motif of a distannametallacycle comprised of a [(NHC)2 M(0) ] fragment and Sn2 Trip4 represent rare higher congeners of the well-known olefin complexes. DFT calculations indicate the presence of a π-type Sn-Sn interaction in these first examples for acyclic distannenes symmetrically coordinating to a zero-valent transition metal.
NHC 加合物的二茂锡（Trip=2,4,6-三异丙基苯基）与零价 Ni、Pd 和 Pt 前体配合物反应，可干净地生成各自的金属配合物，其中含有一个三成员环部分 Sn-Sn-M，同时碳烯转移到金属上，并完全取代起始配体。因此，易于获得的二茂锡 NHC 加合物被证明是具有意外 SnSn 键的过渡金属配合物的有价值前体。这些配合物已通过 X 射线衍射和 NMR 光谱以及 DFT 计算进行了研究。具有 [(NHC)2 M(0) ] 片段和 Sn2 Trip4 的二锡金属环结构基元的化合物代表了众所周知的烯烃配合物的稀有更高同系物。DFT 计算表明，在这些首例非循环二锡烯中存在 π 型 Sn-Sn 相互作用，它们对称地配位到零价过渡金属上。
