4.7 Article

A Room-Temperature Stable Y(II) Aryloxide: Using Steric Saturation to Kinetically Stabilize Y(II) Complexes

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INORGANIC CHEMISTRY
卷 59, 期 5, 页码 3207-3214

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.9b03587

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资金

  1. U.S. National Science Foundation [CHE-1855328]
  2. Friedrich -Alexander-University Erlangen Nurnberg (FAU)
  3. German Federal Ministry of Education and Research (BMBF) [02NUK012C, 02NUK020C, BMBF 03SF0502]

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The utility of the bulky aryloxide ligands 2,6-Ad(2)-4-Me-C6H2O- ((ArO-)-Ar-Ad,Ad,me) and 2,6-Ad(2)-4-t-Bu-C6H2O- (Ad,Ad,t-BuArO-; Ad = 1-adamantyl) for stabilizing the Y(II) ion is reported and compared with the results with 2,6-t-Bu-2-4-Me-C6H2O- (Ar'O-). In contrast to the reduction product obtained from reducing Y(OAr')(3) with potassium graphite, which is only stable in solution for 60 s at room temperature, KC8 reduction of Y(OArAd,Ad,t-Bu)(3) in THE in the presence of 2.2.2-cryptand (crypt) produces the room-temperature stable, crystallographically characterizable Y(II) aryloxide [K(crypt)]-[Y(OArAd,Ad,t-Bu)(3)]. The X-band EPR spectrum at 77 K shows an axial pattern with resonances centered at g(perpendicular to) = 1.97 and g(parallel to) = 2.00 and hyperfine coupling constants of A(perpendicular to) = 156.5 G and A(parallel to) = 147.8 G and at room temperature shows an isotropic pattern with g(iso) = 1.98 and A(iso) = 153.3 G, which is consistent with an S = 1/2 spin system with nuclear spin I = 1/2 for the Y-89 isotope (100% natural abundance).

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