Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, 06520, USA.
Hylleraas Center for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315, Oslo, Norway.
Angew Chem Int Ed Engl. 2017 Oct 9;56(42):13047-13051. doi: 10.1002/anie.201707593. Epub 2017 Sep 6.
We have prepared and fully characterized two isomers of [Ir (dpyp) ] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [Ir (dpyp) ] , which to our knowledge represent the first mononuclear coordination complexes of Ir in an N,O-donor environment. One isomer has been fully characterized in the Ir state, including by X-ray crystallography, XPS, and DFT calculations, all of which confirm metal-centered oxidation. The unprecedented stability of these Ir complexes is ascribed to the exceptional donor strength of the ligands, their resistance to oxidative degradation, and the presence of four highly donor alkoxide groups in a plane, which breaks the degeneracy of the d-orbitals and favors oxidation.
我们已经制备并充分表征了 [Ir(dpyp)] 的两种异构体（dpyp=meso-2,4-二(2-吡啶基)-2,4-戊二酸二酯）。这些配合物可以被氧化为 [Ir(dpyp)]，据我们所知，它们代表了第一个单核配位配合物的 Ir 在 N,O-供体环境中。一个异构体已经在 Ir 状态下进行了全面的表征，包括 X 射线晶体学、XPS 和 DFT 计算，所有这些都证实了金属中心的氧化。这些 Ir 配合物具有前所未有的稳定性，归因于配体的异常供电子强度、它们对氧化降解的抵抗力以及在一个平面上存在四个高度供电子的烷氧基基团，这打破了 d-轨道的简并性并有利于氧化。
