[(η⁶-p-cymene)OsI₂]₂ was found to be a good catalyst for the cyclopropanation reaction of isobutyl vinyl ether with 3-tert-butyldiazoindene. In contrast, the complexes [(η⁶-p-cymene)OsX₂]₂ (X = Cl, Br) are poorer catalysts for the reaction. The interesting halide effect can be related to the tendency of osmium indenylidene complexes [(η⁶-p-cymene)OsX₂(indenylidene)] (6) (derived from the reactions of [(η⁶-p-cymene)OsX₂] (5) with diazoindene, X = Cl, Br, I) to undergo migratory insertion reactions to give η⁵-haloindenyl complexes. While the chloro indenylidene complex 6Cl readily rearranges to the corresponding η⁵-chloroindenyl complex 8Cl, the iodo indenylidene complex 6I can be stored in solutions for weeks without appreciable decomposition. The thermal stability of the bromo indenylidene 6Br is between those of Cl- and I-substituted indenylidenes. Computational studies have been carried out to understand the experimental observations. The indenylidene complexes described here represent the first well-characterized mononuclear indenylidene complexes synthesized from diazoindene precursors.

中文翻译：

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卤化物对In茚基络合物稳定性的影响：分离，表征和反应性。

[（η ⁶ - p -cymene）OSI ₂ ] ₂被发现是用于异丁基乙烯基醚与3-环丙烷化反应中的良好的催化剂叔-butyldiazoindene。相反，配合物[（η ⁶ - p -cymene）OSX ₂ ] ₂（X =氯，溴）是用于该反应较差的催化剂。有趣的卤化物效果可以与锇络合物茚基的倾向[（η ⁶ - p -cymene）OSX ₂（亚茚基）]（6）（从反应衍生[（η ⁶ - p -cymene）OSX ₂ ] （5）用diazoindene，X =氯，溴，I）经历洄游插入反应，得到η ⁵ -haloindenyl络合物。虽然氯亚茚基络合物6Cl容易重新排列到对应的η ⁵ -chloroindenyl复杂8Cl，碘代茚基配合物6I可以存储在解决方案的周而没有明显的分解。溴茚基6Br的热稳定性在C 1和C 1-取代的茚基亚烷基之间。已经进行了计算研究以了解实验观察。本文所述的茚基亚烷基络合物代表从重氮茚前体合成的第一个表征良好的单核茚基亚烷基络合物。