Geometric Control of Nuclearity in Copper(I)/Dioxygen Chemistry
Geometric Control of Nuclearity in Copper(I)/Dioxygen Chemistry
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DOI：
10.1021/ic501461n
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发表时间：
2014-08-18
影响因子：
4.6
通讯作者：
Itoh, Shinobu
中科院分区：
文献类型：
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作者：
Abe, Tsukasa;Morimoto, Yuma;Itoh, Shinobu
合成了由一系列带有刚性环状二胺骨架的 N-3-三齿配体支撑的铜（I）配合物，例如具有共同的 2-（2-吡啶基）乙基侧臂的 1,5-二氮杂环辛烷（L8，八元环）、1,4-二氮杂环己烷（L7，七元环）或 1,4-二氮杂环己烷（L6，六元环），并合成了它们对O-2进行了比较。 L8 的铜(I)络合物优先提供单核铜(II)端接超氧化物络合物S，如先前报道的[Itoh, S., et al. 2017]。 J. Am.化学。苏克。 2009, 131, 2788-2789]，而L7的铜(I)配合物在丙酮中低温（-85℃）下生成双(mu-氧化)二铜(111)配合物O。另一方面，在相同条件下L6的铜(I)络合物的氧化反应中没有检测到这样的活性氧络合物。此外，还检查了无环三齿配体（LA，PyCH2CH2N（CH3）CH2CH2CH2N（CH3）（2）；Py = 2-吡啶基）支持的铜（I）络合物的O-2反应性，以获得（mu-eta（2）：eta（2）-过氧化）二铜（II）络合物P-s和双（mu-氧化）二铜（III）络合物的混合物O.仔细检查铜（I）和铜（II）配合物的晶体结构以及铜（I）配合物的氧化还原电位，揭示了支持配体对控制生成的铜活性氧配合物的核性的重要几何效应。
Copper(I) complexes supported by a series of N-3-tridentate ligands bearing a rigid cyclic diamine framework such as 1,5-diazacyclooctane (L8, eight-membered ring), 1,4-diazacyclohexane (L7, seven-membered ring), or 1,4-diazacyclohexane (L6, six-membered ring) with a common 2-(2-pyridyl)ethyl side arm were synthesized and their reactivity toward O-2 were compared. The copper(I) complex of L8 preferentially provided a mononuclear copper(II) end-on superoxide complex S as reported previously [Itoh, S., et al. J. Am. Chem. Soc. 2009, 131, 2788-2789], whereas a copper(I) complex of L7 gave a bis(mu-oxido)dicopper(111) complex O at a low temperature (-85 degrees C) in acetone. On the other hand, no such active-oxygen complex was detected in the oxygenation reaction of the copper(I) complex of L6 under the same conditions. In addition, O-2-reactivity of the copper(I) complex supported by an acyclic version of the tridentate ligand (LA, PyCH2CH2N(CH3)CH2CH2CH2N(CH3)(2); Py = 2-pyridyl) was examined to obtain a mixture of a (mu-eta(2):eta(2)-peroxido)dicopper(II) complex P-s and a bis(mu-oxido)dicopper(III) complex O. Careful inspection of the crystal structures of copper(I) and copper(II) complexes and the redox potentials of copper(I) complexes has revealed important geometric effects of the supporting ligands on controlling nudearity of the generated copper active-oxygen complexes.