Direct crystallographic observation of a coordinatively unsaturated transition-metal complex in situ generated within a self-assembled cage
Direct crystallographic observation of a coordinatively unsaturated transition-metal complex in situ generated within a self-assembled cage
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DOI：
10.1021/ja0609250
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发表时间：
2006-05-24
影响因子：
15
通讯作者：
Fujita, Makoto
中科院分区：
文献类型：
--
作者：
Kawano, Masaki;Kobayashi, Yasuhiro;Fujita, Makoto
本文报道了一种极不稳定的配位不饱和过渡金属配合物Cp'Mn（CO）_2（Cp' =甲基萘）在低温下在自组装笼的封闭腔中以结晶态生成和捕获的晶体学原位观察结果。稳定的Cp 'Mn（CO）3配位在配位笼的空腔中，CO配体光解生成不稳定的Cp' Mn（CO）2。在低温下被捕获在笼中，Cp'Mn（CO）2显示出足够的稳定性，可以通过X射线晶体学进行分析。衍射研究表明，16-电子不饱和锰配合物采用金字塔的几何形状，而不是一个平面的几何形状。
In situ crystallographic observation of an extremely labile coordinatively unsaturated transition-metal complex, Cp‘Mn(CO)2(Cp‘ = methylcyclopentadienyl), was achieved by generating and trapping it within the confined cavity of a self-assembled cage in the crystalline state at a low temperature. The labile target Cp‘Mn(CO)2was formed by the photodissociation of the CO ligand from stable Cp‘Mn(CO)3, which was accommodated within the cavity of the coordination cage. Being trapped in the cage at a low temperature, Cp‘Mn(CO)2showed sufficient stability to be analyzed by X-ray crystallography. The diffraction study revealed that the 16-electron unsaturated Mn complex adopted a pyramidal geometry rather than a planar geometry.