Unexpected Formation of Ru_2Sn_2 Bicyclic Four-membered Ring Complexes with Butterfly and Inverse-Sandwich Structures
Unexpected Formation of Ru_2Sn_2 Bicyclic Four-membered Ring Complexes with Butterfly and Inverse-Sandwich Structures
复制标题
蝶形和反夹心结构 Ru_2Sn_2 双环四元环配合物的意外形成
DOI：
10.1021/ic302782n
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发表时间：
2013
影响因子：
4.6
通讯作者：
Jing-Dong Guo and Shigeru Nagase
中科院分区：
文献类型：
--
作者：
Takuya Kuwabara;Masaichi Saito;Jing-Dong Guo and Shigeru Nagase
四乙基硫代锡醇1与[Cp*RuCl] 4的反应不是得到η5锡醇双阴离子配合物，而是得到两种新型的双锡亚基桥联双核钌配合物，它们分别具有蝶形和反夹心结构，这取决于[Cp*RuCl] 4与硫代锡醇的化学计量比.发现两种配合物之间的氧化还原行为是可逆的。通过X射线衍射分析确定了分子结构。蝶形配合物的Ru-Ru键为2.3428（6）π，是含Cp或Cp*Ru单元的双核钌配合物中最短的。理论计算表明，Ru-Ru键之所以很短，是因为Ru原子间存在一个σ键，而两个Ru 2Sn环上存在两个离域的三中心键.
Reactions of tetraethyldilithiostannole1with [Cp*RuCl]4afforded not η5-stannole dianion complexes but two novel bis(stannylene)-bridged dinuclear ruthenium complexes, which have butterfly and inverse-sandwich structures, respectively, depending on the stoichiometry of [Cp*RuCl]4toward dilithiostannole. The redox behavior between the two complexes is found to be reversible. The molecular structures were determined by X-ray diffraction analysis. The Ru–Ru bond of the butterfly complex is 2.3428(6) Å, which is the shortest among those of dinuclear ruthenium complexes having Cp or Cp*Ru units. Theoretical calculations revealed that the very short Ru–Ru bond is due to the presence of one σ bond between the ruthenium atoms and two three-centered bonds delocalized over the two Ru2Sn rings.