Department of Chemistry , University of California , Irvine , California 92697-2025 , United States.
Department of Chemistry and Pharmacy, Inorganic Chemistry , Friedrich-Alexander-University Erlangen-Nürnberg , Egerlandstrasse 1 , D-91058 Erlangen , Germany.
Inorg Chem. 2018 Oct 15;57(20):12876-12884. doi: 10.1021/acs.inorgchem.8b02053. Epub 2018 Sep 24.
[Y(N(SiMe))] reacts with (ArOH)mes to form the Y complex [((ArO)mes)Y], 1-Y. This complex reacts with potassium metal in the presence of 2.2.2-cryptand to give a cocrystallized mixture of [K(2.2.2-cryptand)][((ArO)mes)Y], 2-Y, and [K(2.2.2-cryptand)][((ArO)mes)YH], 3-Y. The electron paramagnetic resonance spectrum of this crystalline mixture exhibits an isotropic signal at 77 K ( g = 2.000, W = 1.8 mT), suggesting that 2-Y is best described as a Y complex of the tris(aryloxide)mesitylene radical ((ArO)mes). Evidence of the hydride ligand in 3-Y was obtained by Y-H heteronuclear multiple quantum coherence NMR spectroscopy, and a coupling constant of J = 93 Hz was observed. A single crystal of 3-Y was also obtained in pure form and structurally characterized for comparison with the crystal data on the mixed component 2-Ln/3-Ln crystals. The origin of the hydride in 3-Ln is unknown, but further studies of the reduction of 1-La, previously found to form 2-La, revealed a possible source. Ligand-based C-H bond activation and loss of hydrogen can occur under reducing conditions to form a tetraanionic ligand derived from ((ArO)mes), as observed in [K(2.2.2-cryptand)][((ArO)(CMe(CH)CH)La], 4-La.
[Y(N(SiMe))]与(ArOH)mes 反应生成 Y 配合物[((ArO)mes)Y]，1-Y。该配合物在 2.2.2-穴醚存在下与钾金属反应，生成[K(2.2.2-穴醚)][((ArO)mes)Y]，2-Y 和[K(2.2.2-穴醚)][((ArO)mes)YH]，3-Y 的共结晶混合物。该结晶混合物的电子顺磁共振谱在 77 K 下显示出各向同性信号（g = 2.000，W = 1.8 mT），表明 2-Y 最好被描述为三(芳氧基)mesitylene 自由基((ArO)mes)的 Y 配合物。3-Y 中存在氢化物配体的证据是通过 Y-H 异核多量子相干 NMR 光谱获得的，观察到耦合常数 J = 93 Hz。还获得了 3-Y 的单晶，并对其进行了结构表征，以便与混合组分 2-Ln/3-Ln 晶体的晶体数据进行比较。3-Ln 中氢化物的来源尚不清楚，但对先前发现形成 2-La 的 1-La 的还原进一步研究揭示了可能的来源。在还原条件下，配体上的 C-H 键可以发生活化和失去氢，形成源自((ArO)mes)的四阴离子配体，如在[K(2.2.2-穴醚)][((ArO)(CMe(CH)CH)La]，4-La 中观察到的那样。
