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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Molecular Structures of Some syn-[1.1]Metallocenophanes, anti-Ferrocenium [1.1]ruthenocenophane, and Their NMR Spectroscopies
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Molecular Structures of Some syn-[1.1]Metallocenophanes, anti-Ferrocenium [1.1]ruthenocenophane, and Their NMR Spectroscopies

机译：某些顺式[1.1]金属间苯二酚，抗二茂铁[1.1]钌烯十一烷的分子结构及其NMR光谱学

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摘要

The structures of ferroceno [1.1] ruthenocenophane-1,13-dione (1a) and related compounds have been analyzed by X-ray diffraction. The crystal form of 1a is orthorhombic, space group Pbc2_1, a = 6.0660(3), b = 13.371(1), c = 19.420(2) A, V = 1575.1(2) A~3, and the final R = 0.043 and R_w = 0.054. The air-oxidation of ferroceno [1.1] ruthenocenophane (2a) in xylene at 400 K gives ferroceno [1.1] ruthenocenophane-1-one (3a), implying the oxidation of the methylene group to a carbonyl group. The crystal form of 3a is orthorhombic, space group Pbn2_1, a = 7.6460(7), b = 10.708(1), c = 19.587(2) A, V = 1603.7(3) A~3, and the final R = 0.052 and R_w = 0.051. The same oxidation is found for [1.1] ferocenophane (2b) giving [1.1] ferrocenophane-1-one (3b). The crystal form of 3b is orthorhomibic, space group Pbnm, a = 7.5460(9), b = 10.6560(6), c = 19. 8290(7) A. V = 1594.4(2) A~3, and the final R = 0.070 and R_w = 0.077. All the structural data of 1a, 3a, and 3b showed their syn conformation about two bridging methylene groups and rigid structures caused by the good planarity of C_5H_4COC_5H_4 and C_5H_4CH_2C_5H_4 planes. These rigid structural features give remarkable variable temperature NMR (VT-NMR) spectra caused by the appropriate rate constant of syn_a <-> syn_b motion in solutions. The ΔG~(++) (Tc) values of the motion are estimated to be about 60 kJ mol~(-1), which is more than six times larger than those of 2a and 2b. The anti-form of ferrocenium [1.1] ruthenocenophane formulated as [Fe~(III)(C_5H_4CH_2C_5H_4)_2Ru~(II)]PF_6 (4) was prepared by the oxidation of syn-form 2a in sulfuric acid containing NH_4PF_6. This is the first example of the oxidative occurrence of the conformational change from syn- to anti-form. The crystal form of 4 is triclinic, space group P1, a = 9.350(2), b = 10. 777(3), c = 10. 980(3) A, α = 91.84(3)°, β = 96. 66(2)°, γ = 111.12(2)°, V = 1021. 8(5) A~3 and the final R = 0.044 and R_w = 0.048. The cation contains largely twisted C_5H_4CH_2C_5H_4 plane (the twist angle, 34.1—38.5°) and largely tilted and rotated Cp-rings of the Ru (C_5H_4)_2 moiety.
机译：X射线衍射分析了二茂铁[1.1]钌烯十一烷-1,13-二酮（1a）和相关化合物的结构。 1a的晶体形式为正交晶，空间群Pbc2_1，a = 6.0660（3），b = 13.371（1），c = 19.420（2）A，V = 1575.1（2）A〜3，最终R = 0.043并且R_w ＝ 0.054。在二甲苯中于400 K空气氧化二茂铁[1.1]钌钌甲壳烷（2a）生成二茂铁[1.1]钌烯十一烷-1-酮（3a），这意味着亚甲基被氧化为羰基。 3a的晶型是正交晶体，空间群Pbn2_1，a = 7.6460（7），b = 10.708（1），c = 19.587（2）A，V = 1603.7（3）A〜3，最终R = 0.052并且R_w = 0.051。对于[1.1]二茂铁oph（2b）发现相同的氧化，得到[1.1]二茂铁oph-1-酮（3b）。 3b的晶体形式为正交晶，空间群为Pbnm，a = 7.5460（9），b = 10.6560（6），c = 19.8290（7）A.V = 1594.4（2）A〜3，最后的R = 0.070和R_w = 0.077。 1a，3a和3b的所有结构数据均显示出它们由于C_5H_4COC_5H_4和C_5H_4CH_2C_5H_4平面的良好平面性而在两个桥连的亚甲基和刚性结构上的顺式构象。这些刚性的结构特征给出了由溶液中syn_a-syn_b运动的适当速率常数引起的显着的可变温度NMR（VT-NMR）光谱。估计运动的ΔG〜（++）（Tc）值约为60 kJ mol〜（-1），是2a和2b的两倍以上。通过在含有NH_4PF_6的硫酸中氧化合成形式2a来制备配制成[Fe〜（III）（C_5H_4CH_2C_5H_4）_2Ru〜（II）] PF_6（4）的二茂铁铈[1.1]钌烯十一烷的抗形式。这是构象从顺式转变为反式的氧化发生的第一个例子。 4的晶型是三斜晶，空间群P1，a = 9.350（2），b = 10.777（3），c = 10.980（3）A，α= 91.84（3）°，β= 96。 66（2）°，γ＝ 111.12（2）°，V ＝ 1021。8（5）A〜3，最终R ＝ 0.044，R_w ＝ 0.048。阳离子包含大量扭曲的C_5H_4CH_2C_5H_4平面（扭曲角为34.1-38.5°）以及Ru（C_5H_4）_2部分的大部分倾斜和旋转的Cp环。

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