Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616, United States.
J Am Chem Soc. 2020 Dec 30;142(52):21634-21639. doi: 10.1021/jacs.0c10958. Epub 2020 Dec 15.
High-valent transition metal-oxo, -peroxo, and -superoxo complexes are crucial intermediates in both biological and synthetic oxidation of organic substrates, water oxidation, and oxygen reduction. While high-valent oxygenated complexes of Mn, Fe, Co, and Cu are increasingly well-known, high-valent oxygenated Ni complexes are comparatively rarer. Herein we report the isolation of such an unusual high-valent species in a thermally unstable Ni(μ-1,2-peroxo) complex, which has been characterized using single-crystal X-ray diffraction and X-ray absorption, NMR, and UV-vis spectroscopies. Reactivity studies show that this complex is stable toward dissociation of oxygen but reacts with simple nucleophiles and electrophiles.
高价过渡金属-氧，-过氧和-超氧配合物是生物和有机底物合成氧化、水氧化和氧还原中至关重要的中间体。虽然 Mn、Fe、Co 和 Cu 的高价含氧配合物越来越为人所知，但高价含氧 Ni 配合物则相对较少。在此，我们报道了在热不稳定的 Ni(μ-1,2-过氧)配合物中分离到的这种不寻常的高价物种，该物种已通过单晶 X 射线衍射、X 射线吸收、NMR 和紫外可见光谱进行了表征。反应性研究表明，该配合物对氧的离解稳定，但与简单的亲核试剂和亲电试剂反应。
