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Molecular Cu~(II)-O-Cu~(II) Complexes: Still Waters Run Deep

机译:分子Cu〜(II)-O-Cu〜(II)配合物:静水深流

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摘要

Research on O2 activation at ligated Cu~i is fueled by its biological relevance and the quest for efficient oxidation catalysts. A rarely observed reaction is the formation of a Cu~(II)-O-Cu~(II) species, which is more special than it appears at first sight: a single oxo ligand between two Cu~(II) centers experiences considerable electron density, and this makes the corresponding complexes reactive and difficult to access. Hence, only a small number of these compounds have been synthesized and characterized unequivocally to date, and as biological relevance was not apparent, they remained unappreciated. However, recently they moved into the spotlight, when Cu~(II)-O-Cu~(II) cores were proposed as the active species in the challenging oxidation of methane to methanol at the surface of a Cu-grafted zeolite and in the active center of the copper enzyme particulate methane monooxygenase. This Minireview provides an overview of these systems with a special focus on their reactivity and spectroscopic features.
机译:由于其生物学意义和对高效氧化催化剂的追求,推动了在固结Cu〜i上O2活化的研究。很少观察到的反应是形成Cu〜(II)-O-Cu〜(II)物种,这种现象比乍看起来更特殊:两个Cu〜(II)中心之间的一个氧代配体会经历大量电子密度高,这使得相应的配合物具有反应性且难以接近。因此,迄今为止,仅合成了少量这些化合物,并对其进行了明确的表征,并且由于生物学相关性尚不明显,因此它们仍然未被人们认识。然而,近来,当有人提出将Cu〜(II)-O-Cu〜(II)核作为挑战性的甲烷在接枝沸石表面和接枝沸石表面上的甲烷氧化为甲醇的活性物种时,它们成为人们关注的焦点。铜酶颗粒甲烷单加氧酶的活性中心。本Minireview提供了这些系统的概述,特别着重于它们的反应性和光谱特性。

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