Synthesis, Structures, and Reactivities of Iron Complexes Bearing an Isoindoline‐Based, Polyprotic Pincer‐Type Pyrazole Ligand
Synthesis, Structures, and Reactivities of Iron Complexes Bearing an Isoindoline‐Based, Polyprotic Pincer‐Type Pyrazole Ligand
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带有异吲哚啉基多质子钳型吡唑配体的铁配合物的合成、结构和反应性
DOI：
10.1002/zaac.202100103
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Kuwata Shigeki
中科院分区：
文献类型：
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作者：
Toda Tatsuro;Kuwata Shigeki
研究了源自 1,3-双(吡唑-3-基亚氨基)异吲哚啉1的多质子 NNN 钳型双(吡唑)铁配合物的合成和性质。当1用氯化铁(II)处理时，得到顺磁性方形锥体络合物[FeCl2(LH3)](2; LH3=3-(5-叔丁基吡唑-3-基氨基)-1-(5-叔丁基吡唑-3-基亚氨基)-1H-异吲哚)。 2 与两当量的反应三氟甲磺酸银，然后添加两当量。三甲基膦产生抗磁性八面体络合物 [Fe(OTf)(PMe3)2(LH3)]OTf (3)，将其转化为羰基络合物 [Fe(CO)(PMe3)2(LH3)](OTf)2(4)。用三乙胺处理 4 导致螯合物主链去质子化，得到异吲哚啉-2-基络合物 [Fe(CO)(PMe3)2(LH2)]OTf (5)。对LH3和LH2配体的结构进行了详细比较。 2-5 中的钳配体中的 NH 基团伴随着氢键，显示出其布朗斯台德酸性。此外，3催化肼的歧化，尽管催化活性低于相关的基于吡啶的钳络合物6 a。
The synthesis and properties of polyprotic NNN pincer‐type bis(pyrazole) iron complexes derived from a 1,3‐bis(pyrazol‐3‐ylimino)isoindoline1were investigated. When1was treated with iron(II) chloride, the paramagnetic, square‐pyramidal complex [FeCl2(LH3)] (2; LH3=3‐(5‐tert‐butylpyrazol‐3‐ylamino)‐1‐(5‐tert‐butylpyrazol‐3‐ylimino)‐1H‐isoindole) was obtained. Reaction of2with two equiv. of silver triflate followed by addition of two equiv. of trimethylphosphine yielded the diamagnetic, octahedral complex [Fe(OTf)(PMe3)2(LH3)]OTf (3), which was converted to the carbonyl complex [Fe(CO)(PMe3)2(LH3)](OTf)2(4). Treatment of4with triethylamine led to deprotonation of the chelate backbone to give the isoindolin‐2‐yl complex [Fe(CO)(PMe3)2(LH2)]OTf (5). The structures of the LH3and LH2ligands were compared in details. The NH groups in the pincer ligand in2–5are accompanied by hydrogen bonds, showing their Brønsted acidic nature. In addition,3catalyzed disproportionation of hydrazine, although the catalytic activity was lower than that of a related pyridine‐based pincer complex6 a.