Moehring Samuel A, Miehlich Matthias, Hoerger Christopher J, Meyer Karsten, Ziller Joseph W, Evans William J
Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University, Erlangen-Nürnberg (FAU), Egerlandstrasse 1, 91058 Erlangen, Germany.
Inorg Chem. 2020 Mar 2;59(5):3207-3214. doi: 10.1021/acs.inorgchem.9b03587. Epub 2020 Feb 12.
The utility of the bulky aryloxide ligands 2,6-Ad-4-Me-CHO (ArO) and 2,6-Ad-4--Bu-CHO (ArO; Ad = 1-adamantyl) for stabilizing the Y(II) ion is reported and compared with the results with 2,6--Bu-4-Me-CHO (Ar'O). In contrast to the reduction product obtained from reducing Y(OAr') with potassium graphite, which is only stable in solution for 60 s at room temperature, KC reduction of Y(OAr) in THF in the presence of 2.2.2-cryptand (crypt) produces the room-temperature stable, crystallographically characterizable Y(II) aryloxide [K(crypt)][Y(OAr)]. The X-band EPR spectrum at 77 K shows an axial pattern with resonances centered at = 1.97 and = 2.00 and hyperfine coupling constants of = 156.5 G and = 147.8 G and at room temperature shows an isotropic pattern with = 1.98 and = 153.3 G, which is consistent with an = 1/2 spin system with nuclear spin = 1/2 for the Y isotope (100% natural abundance).
报道了庞大的芳氧基配体2,6-金刚烷基-4-甲基-CHO（ArO）和2,6-金刚烷基-4-叔丁基-CHO（ArO；Ad = 1-金刚烷基）对稳定Y（II）离子的效用，并与2,6-叔丁基-4-甲基-CHO（Ar'O）的结果进行了比较。与用石墨钾还原Y（OAr'）得到的还原产物不同，后者在室温下仅在溶液中稳定60秒，在2.2.2-穴醚（穴醚）存在下，在四氢呋喃中用KC还原Y（OAr）会生成室温稳定的、可通过晶体学表征的Y（II）芳氧基化合物[K（穴醚）][Y（OAr）]。77K下的X波段电子顺磁共振谱显示出轴向模式，共振中心位于g = 1.97和g = 2.00，超精细耦合常数为A = 156.5G和A = 147.8G，室温下显示出各向同性模式，g = 1.98和A = 153.3G，这与Y同位素（天然丰度100%）核自旋I = 1/2的S = 1/2自旋体系一致。
