Qi Ru-Yi, Corbett John D.
Department of Chemistry, Iowa State University, Ames, Iowa 50011.
Inorg Chem. 1997 Dec 17;36(26):6039-6044. doi: 10.1021/ic970818u.
Suitable reactions of ABr, Zr, ZrBr(4), and an interstitial Z element in Ta containers at 850 degrees C afford two series of quaternary cluster phases containing A(4)Br(3+) ions. Cubic (A(4)Br)(2)Zr(6)(Z)Br(18) phases occur for various combinations of A = Na-Cs, Z = Be, B, H, Mn. The combination with A = K, Z = B was structurally characterized (inverse fluorite, Fm&thremacr;m, Z = 4, a = 16.191(2) Å). The 15-e cluster exhibits the appropriate magnetic moment, and this decreases toward the diamagnetic 14-electron limit in products with potassium deficiencies, (K(4)(-)(x)())(2)Zr(6)Br(18)B, x </= approximately 0.5. The tetragonal Cs(4)Br[Zr(6)(B)Br(12)]Br(4) (P&fourmacr;2(1)m, Z = 2, a = 12.5482(7) Å, c = 11.5610(9) Å) contains a new type of puckered M(6)Br(16) layers with Cs(4)Br(3+) in tunnels normal to the layers. Both examples of A(4)Br(3+) ions have short central Br-A bonds plus three to nine more distant bromines in neighboring clusters about each A, respectively.
在850摄氏度下，ABr、Zr、ZrBr₄和间隙Z元素在钽容器中发生的合适反应产生了两个系列的含A₄Br₃⁺离子的四元簇相。对于A = Na - Cs、Z = Be、B、H、Mn的各种组合，会出现立方相(A₄Br)₂Zr₆(Z)Br₁₈。对A = K、Z = B的组合进行了结构表征（反萤石结构，Fm&thremacr;m，Z = 4，a = 16.191(2) Å）。15电子簇具有合适的磁矩，在缺钾产物(K₄⁻ₓ)₂Zr₆Br₁₈B（x ≤ 约0.5）中，该磁矩朝着抗磁性的14电子极限降低。四方相Cs₄Br[Zr₆(B)Br₁₂]Br₄（P&fourmacr;2₁m，Z = 2，a = 12.5482(7) Å，c = 11.5610(9) Å）包含一种新型的褶皱M₆Br₁₆层，Cs₄Br₃⁺位于垂直于层的隧道中。A₄Br₃⁺离子的这两个例子都有短的中心Br - A键，并且每个A在相邻簇中分别还有三到九个更远的溴原子。
