Structure and Reactivity of Copper Complexes Supported by a Bulky Tripodal N4 Ligand: Copper(I)/Dioxygen Reactivity and Formation of a Hydroperoxide Copper(II) Complex
Structure and Reactivity of Copper Complexes Supported by a Bulky Tripodal N4 Ligand: Copper(I)/Dioxygen Reactivity and Formation of a Hydroperoxide Copper(II) Complex
复制标题
大体积三足 N4 配体支持的铜配合物的结构和反应性：铜 (I)/分子氧反应性和氢过氧化物铜 (II) 配合物的形成
DOI：
10.1002/zaac.201800083
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发表时间：
2018
影响因子：
1.4
通讯作者：
and S. Itoh
中科院分区：
文献类型：
--
作者：
S. Paria;T. Ohta;Y. Morimoto;H. Sugimoto;T. Ogura;and S. Itoh
配合物 [(susan){FeIII(OAc)(μ-O)FeIII(OAc)}](ClO4)2、[(susan){FeIII(μ-O)(μ-OAc)FeIII}](ClO4)3 和 [(susan){FeIII(μ-O)(μ-CO3)FeIII}](ClO4)2(susan =合成并表征了4,7-二甲基-1,1,10,10-四(2-吡啶甲基)-1,4,7,10-四氮杂烷)。显着的红外振动不会从固态转移到 CH3CN 溶液，表明无需结构重排或取代即可溶解。 [(susan){FeIII(OAc)(μ-O)FeIII(OAc)}]2+ 中的乙酸盐处于反式构象，导致中心核心和整体复合物的 C2 对称性。另一方面，第二个桥接配体强制中央核心的 aC 对称性，这与配体围绕中央核心的包裹不可通约，导致仅产生整体 C1 对称性。末端乙酸酯 (1.93 Å) 的 Fe-OAc 键比桥接乙酸酯 (1.97 和 2.07 Å) 短。桥联双阴离子碳酸盐也会产生较短的 Fe-O 碳键（1.91 和 1.97 Å）。穆斯堡尔谱显示 [(susan){FeIII(μ-O)(μ-CO3)FeIII}](ClO4)2 的四极分裂较低，与较短且共价较多的 Fe-O 碳键一致。单桥和双桥配合物的 UV/Vis/NIR 光谱在 d-d 和 LMCT 区域有所不同。电化学表征显示氧化和还原电位的变化。根据 π 供体相互作用和复合物总电荷的差异讨论了这种变化。
The complexes [(susan){FeIII(OAc)(μ‐O)FeIII(OAc)}](ClO4)2, [(susan){FeIII(μ‐O)(μ‐OAc)FeIII}](ClO4)3, and [(susan){FeIII(μ‐O)(μ‐CO3)FeIII}](ClO4)2(susan = 4,7‐dimethyl‐1,1,10,10‐tetra(2‐pyridylmethyl)‐1,4,7,10‐tetraazadecane) were synthesized and characterized. Prominent IR vibrations do not shift from the solid state to CH3CN solutions demonstrating dissolution without structural rearrangements or substitutions. The acetates in [(susan){FeIII(OAc)(μ‐O)FeIII(OAc)}]2+are in atransconformation resulting in aC2symmetry of the central core and the overall complex. On the other hand, a second bridging ligand enforces aCSsymmetry of the central core, which is incommensurable with the wrapping of the ligand around the central core resulting in only overallC1symmetry. The Fe–OAcbonds are shorter for the terminal acetates (1.93 Å) than for the bridging acetate (1.97 and 2.07 Å). The bridging dianionic carbonate also results in shorter Fe–Ocarbbonds (1.91 and 1.97 Å). Mössbauer spectroscopy shows a lower quadrupole splitting for [(susan){FeIII(μ‐O)(μ‐CO3)FeIII}](ClO4)2in line with the shorter and thus more covalent Fe–Ocarbbonds. UV/Vis/NIR spectra differ in the d–d and in the LMCT regions for the mono‐ and doubly‐bridged complexes. The electrochemical characterization shows variations for the potentials for oxidations and reductions. This variation is discussed in light of the difference inπ‐donor interactions and the overall charge of the complexes.