Goicoechea Jose M, Hull Michael W, Sevov Slavi C
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
J Am Chem Soc. 2007 Jun 27;129(25):7885-93. doi: 10.1021/ja071044b. Epub 2007 Jun 6.
Reactions of ethylenediamine solutions of K4Bi5 with Ni(PPh3)2(CO)2 yielded four novel hetero-atomic Bi/Ni deltahedral clusters. Three of them, the 7-atom pentagonal bipyramidal [Bi3Ni4(CO)6]3-, the 8-atom dodecahedral [Bi4Ni4(CO)6]2-, and the Ni-centered or empty 12-atom icosahedral [Nix@[Bi6Ni6(CO)8]4-, are closo-species according to both electron count and shape. The centered icosahedral cluster resembles packing in intermetallic compounds and belongs to the emerging class of intermetalloid clusters. The shape of the fourth cluster, [Bi3Ni6(CO)9]3-, can be derived from the icosahedral Ni-centered [Ni@[Bi6Ni6(CO)8]4- by removal of three Bi- and one Ni-atoms of two neighboring triangular faces. The clusters were structurally characterized by single-crystal X-ray diffraction in compounds with potassium cations sequestered by 2,2,2-crypt or 18-crown-6 ether. They were also characterized in solution by electrospray mass spectrometry.
K4Bi5的乙二胺溶液与Ni(PPh3)2(CO)2反应生成了四个新型杂原子Bi/Ni三角面体簇合物。其中三个，7原子的五角双锥[Bi3Ni4(CO)6]3-、8原子的十二面体[Bi4Ni4(CO)6]2-以及以Ni为中心或中空的12原子二十面体[Nix@[Bi6Ni6(CO)8]4-，根据电子计数和形状均为闭合型物种。中心二十面体簇合物类似于金属间化合物中的堆积结构，属于新兴的类金属间簇合物类别。第四个簇合物[Bi3Ni6(CO)9]3-的形状可由以Ni为中心的二十面体[Ni@[Bi6Ni6(CO)8]4-通过去除两个相邻三角形面的三个Bi原子和一个Ni原子得到。这些簇合物在结构上通过单晶X射线衍射在由2,2,2-穴醚或18-冠-6醚螯合钾阳离子的化合物中进行了表征。它们在溶液中也通过电喷雾质谱进行了表征。
