Inorganic Chemistry II, Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstraße 150, 44780, Bochum, Germany.
Dalton Trans. 2013 Aug 7;42(29):10540-4. doi: 10.1039/c3dt51230d. Epub 2013 Jun 13.
Zn-Cp* bond cleavage reactions leading to novel monovalent cationic zinc species are presented (Cp* = pentamethylcyclopentadienyl). The treatment of [Zn2Cp2] with two equiv. of [H(Et2O)2][BAr4(F)] (BAr4(F) = B{C6H3(CF3)2}4) yields the triple-decker complex [Cp3Zn4(Et2O)2][BAr4(F)] (1) via protolytic removal of a Cp* ligand as CpH, whereas the reaction with an equimolar amount of [FeCp2][BAr4(F)] (Cp = cyclopentadienyl) results in the formation of [CpZn2(Et2O)3][BAr4(F)] (2) under oxidative cleavage of a Cp* ring giving decamethylfulvalene, (Cp*)2, and [FeCp2] as by-products. The molecular structures of compounds 1 and 2 are established by single-crystal X-ray diffraction studies. A new synthetic pathway for the formation of [Zn2Cp2] based on the reductive elimination of CpH from in situ formed Cp*ZnH is presented.
呈现了导致新型单价阳离子锌物种的 Zn-Cp* 键断裂反应（Cp* = 五甲基环戊二烯基）。用两当量的 [H(Et2O)2][BAr4(F)]（BAr4(F) = B{C6H3(CF3)2}4）处理 [Zn2Cp2]，通过质子化去除 Cp 配体作为 CpH，生成三重堆积配合物 [Cp3Zn4(Et2O)2][BAr4(F)]（1），而与等摩尔量的 [FeCp2][BAr4(F)]（Cp = 环戊二烯基）反应，在氧化断裂 Cp* 环的情况下生成十甲基富瓦烯，（Cp*）2 和 [FeCp2] 作为副产物。通过单晶 X 射线衍射研究确定了化合物 1 和 2 的分子结构。提出了一种基于原位形成的 CpZnH 中 CpH 的还原消除形成 [Zn2Cp*2] 的新合成途径。
