终端铱氮三键的氧化还原非惰性行为。
Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2-) Triple Bond.
机构信息
Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
出版信息
Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13169-13173. doi: 10.1002/anie.201607648.
Abstract
The synthesis of the first terminal Group 9 hydrazido(2-) complex, CpIrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir-N triple bond, similar to Bergman's seminal CpIr(N Bu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the N lone pair. Treatment of 6 with MeI results in electron transfer from N to Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally Ir metal center through a hydrazido(2-)/isodiazene valence tautomerization.
摘要
首次合成了第一组 9 族肼基（2-）配合物 CpIrN(TMP)（6）（TMP=2,2,6,6-四甲基哌啶）。电子结构和 X 射线衍射分析表明，该配合物含有一个 Ir-N 三键，类似于 Bergman 开创性的 CpIr(N Bu)亚胺配合物。然而，与 Bergman 的亚胺形成鲜明对比的是，由于 N 孤对电子的存在，6 表现出显著的氧化还原非惰性反应性。用 MeI 处理 6 导致 N 向 Ir 的电子转移，然后 MeI 发生氧化加成到铱中心。这种行为为在形式上的 Ir 金属中心通过肼基（2-）/异二氮烯价态互变异构体进行简便的氧化反应开辟了可能性。
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