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An Unusual (10,3)-a Racemic Twofold Interpenetrating Network Assembled from Isolable Tris(cyclopentadienyl)manganate and Cesocene Building Blocks

机译:由可分离的三(环戊二烯基)锰酸酯和始新世构件组装而成的异常(10,3)-外消旋双重互穿网络

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The syntheses and X-ray crystal structures of [([18]crown-6)_2Cs]~+-[Cp_3Mn]~- )1), [([18]crown-6)_2Cs]~+-[Cp'_3Mn]~_ (2), [CsCp'] (3), [(CsCp')_2-([18]crown-6-] (4), and Cs[MnCp_3] (5), and the synthesis of Cs[MnCp'_3] (6) are reported (Cp' = C_5H_4Me). The anions [Cp_3Mn]~- (1~-) and [Cp'_3Mn]~- (2~-) are characterized by #eta#~2 coordination of all three Cp or Cp' rings. Measurements of the matnetic susceptibilities #CHI#_M resulted in value sof #mu#_eff = 6.20 #mu#_B (300 K), #mu#_eff = 6.33 #mu#_B (301 K), and #mu#_eff = 5.83 #mu#_B (300 K) for 1, 2, and 5, respectively, which are indiative of high-spin d~5-Mn~(2+) centers. Density functional calculations illustrate that the coordination mode of 1~- is characteristic for its sextet electronic ground state. Compound 3 forms infinite chains of cesocene-type sandwiches in the solid state, which are broken up into smal subunits by the addition of crown ether to form 4. Compound 5 is a rare example of a (10,3)-a racemic interpenetrating network that crytallizes in the orthorhombic space group Pbca.
机译:[([18] crown-6)_2Cs]〜+-[Cp_3Mn]〜-)1),[([18] crown-6)_2Cs]〜+-[Cp'_3Mn的合成及X射线晶体结构]〜_(2),[CsCp'](3),[(CsCp')_ 2-([18] crown-6-](4)和Cs [MnCp_3](5),以及Cs [报告了MnCp'_3](6)(Cp'= C_5H_4Me),阴离子[Cp_3Mn]〜-(1〜-)和[Cp'_3Mn]〜-(2〜-)的特征是#eta#〜2配位三个Cp或Cp'环中的每个。磁化率#CHI#_M的测量结果为sof#mu#_eff = 6.20#mu#_B(300 K),#mu#_eff = 6.33#mu#_B(301 K ),而#mu#_eff = 5.83#mu#_B(300 K)分别表示1、2和5,它们是高旋转d〜5-Mn〜(2+)中心的指示。化合物3形成固态的二十四碳烯型三明治的无穷链,并通过添加冠醚将其分解为小亚基,从而形成化合物4。 5是(10,3)-外消旋互穿素的罕见例子在正交空间群Pbca中结晶的g网络。

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