Braunschweig Holger, Ewing William C, Ghosh Sundargopal, Kramer Thomas, Mattock James D, Östreicher Sebastian, Vargas Alfredo, Werner Christine
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email:
Department of Chemistry , Indian Institute of Technology Madras , Chennai 600 036 , India.
Chem Sci. 2016 Jan 1;7(1):109-116. doi: 10.1039/c5sc03206g. Epub 2015 Oct 20.
Treatment of an anionic dimanganaborylene complex ([{Cp(CO)Mn}B]) with coinage metal cations stabilized by a very weakly coordinating Lewis base (SMe) led to the coordination of the incoming metal and subsequent displacement of dimethylsulfide in the formation of hexametalladiborides featuring planar four-membered MB cores (M = Cu, Au) comparable to transition metal clusters constructed around four-membered rings composed solely of coinage metals. The analogies between compounds consisting of BM units and M (M = Cu, Au) units speak to the often overlooked metalloid nature of boron. Treatment of one of these compounds (M = Cu) with a Lewis-basic metal fragment (Pt(PCy)) led to the formation of a tetrametallaboride featuring two manganese, one copper and one platinum atom, all bound to boron in a geometry not yet seen for this kind of compound. Computational examination suggests that this geometry is the result of d-d dispersion interactions between the copper and platinum fragments.
用一种由极弱配位的路易斯碱（SMe）稳定的货币金属阳离子处理阴离子二锰硼烯配合物（[{Cp(CO)Mn}B]），会导致进入的金属发生配位，并在形成具有平面四元MB核（M = Cu，Au）的六金属二硼化物的过程中使二甲基硫醚发生取代，这种六金属二硼化物与仅由货币金属构成的四元环周围构建的过渡金属簇类似。由BM单元和M（M = Cu，Au）单元组成的化合物之间的相似性表明硼的类金属性质常常被忽视。用路易斯碱性金属片段（Pt(PCy)）处理其中一种化合物（M = Cu），会形成一种四金属硼化物，其包含两个锰原子、一个铜原子和一个铂原子，所有这些原子都以一种此类化合物尚未见过的几何构型与硼相连。计算研究表明，这种几何构型是铜和铂片段之间d-d色散相互作用的结果。
