氧化还原活性配体介导的铀酰功能化：通过酰化生成 O-C 键。
Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O-C Bonds via Acylation.
机构信息
H.C. Brown Laboratory, Department of Chemistry , Purdue University , West Lafayette , Indiana 47907 , United States.
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
出版信息
J Am Chem Soc. 2019 Jan 16;141(2):1016-1026. doi: 10.1021/jacs.8b11302. Epub 2019 Jan 4.
A series of uranyl compounds with the redox-active iminoquinone ligand have been synthesized, and their electronic structures elucidated using multinuclear NMR, EPR, electronic absorption spectroscopies, SQUID magnetometry, and X-ray crystallography. Characterization and analysis of the iminoquinone (iq) complex, (iq)UO(OTf)THF (1-iq), the iminosemiquinone (isq) complex, (isq)UOTHF (2-isq), and the amidophenolate (ap) complex, [(ap)UOTHF][K(18-crown-6)(THF)](3-ap crown) show that reduction events are ligand-based, with the uranium center remaining in the hexavalent state. Reactivity of 2-isq with B-chlorocatecholborane or pivaloyl chloride leads to U-O bond scission and reduction of U(VI) to U(IV) concomitant with ligand oxidation along with organic byproducts. O isotopic labeling experiments along with IR spectroscopy, mass spectrometry, and multinuclear NMR spectroscopy confirm that the organic byproducts contain oxygen atoms which originate from U-O bond activation.
已合成了一系列具有氧化还原活性亚氨基醌配体的铀化合物，并使用多核 NMR、EPR、电子吸收光谱、SQUID 磁强计和 X 射线晶体学对其电子结构进行了阐明。对亚氨基醌（iq）配合物（iq）UO（OTf）THF（1-iq）、亚氨基半醌（isq）配合物（isq）UOTHF（2-isq）和酰胺苯氧酸盐（ap）配合物[(ap)UOTHF][K(18-冠-6)(THF)]（3-ap 冠）的表征和分析表明，还原事件是配体基的，铀中心保持六价态。2-isq 与 B-氯代儿茶硼烷或特戊酰氯的反应导致 U-O 键断裂和 U(VI)还原为 U(IV)，同时伴随着配体氧化和有机副产物。O 同位素标记实验以及红外光谱、质谱和多核 NMR 光谱证实，有机副产物含有氧原子，这些氧原子来源于 U-O 键的活化。
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