Synthesis and Structural Trends in Pentafluorophenyl-Substituted Ferrocenes, 1,4-Tetrafluorophenylene-Linked Diferrocenes, and 1,1‘-Ferrocenylene−1,4-Tetrafluorophenylene Co-oligomers

Synthesis and Structural Trends in Pentafluorophenyl-Substituted Ferrocenes, 1,4-Tetrafluorophenylene-Linked Diferrocenes, and 1,1‘-Ferrocenylene−1,4-Tetrafluorophenylene Co-oligomers
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五氟苯基取代的二茂铁、1,4-四氟亚苯基连接的二茂铁和 1,1-二茂铁−1,4-四氟亚苯基共聚低聚物的合成和结构趋势

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发表时间:
2000
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通讯作者:
F. Fronczek
F. Fronczek
中科院分区:
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文献类型:
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作者:
P. A. Deck;M. Lane;and Jennifer L. Montgomery;C. Slebodnick;F. Fronczek

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1,1 '-二硫代二茂铁或(CpLi)2Fe(1)与过量的C6 F6在THF中反应,主要得到(C6 F5 Cp)2Fe(2),伴随着二铁络合物(C6 F5 Cp)FeCp(1,4-C6 F4)CpFe(CpC 6 F5)(3)。1与1.0当量的C6 F6反应,得到微溶的逐步增长低聚物的混合物,归属于[-FeCp(1,4-C6 F4)-]n(4)。[1-Li-2-RNCp]FeCp(6,RN = CH 2NMe 2)与1当量的C6 F6反应,得到[1-(C6 F5)-2-RNCp]FeCp(7)。络合物6与0.5当量的C6 F6反应,得到CpFe[2-RNCp](1,4-C6 F4)[2-RNCp]FeCp,其为两种非对映异构体(内消旋-8,主要和dl-8,次要)的混合物。内消旋-8的相对立体化学通过相应的双(甲基碘)(12)的晶体学分析确定。[1-Li-2-RNCp]Fe(CpLi)(9)与过量的C6 F6反应,主要得到二芳基化的二茂铁[1-(C6 F5)-2-RNCp]Fe(CpC 6 F5)(10)。9与1.0当量的C6 F6反应,得到分子式为[-(2-RNCp)FeCp(1,4-C6 F4)-]n(11)的低聚物的混合物。与4相比,11对于...
1,1‘-Dilithioferrocene, or (CpLi)2Fe (1), reacts with excess C6F6 in THF to afford mostly (C6F5Cp)2Fe (2), accompanied by the diiron complex (C6F5Cp)FeCp(1,4-C6F4)CpFe(CpC6F5) (3). The reaction of 1 with 1.0 equiv of C6F6 affords a mixture of sparingly soluble step-growth oligomers assigned to [−FeCp(1,4-C6F4)−]n (4). [1-Li-2-RNCp]FeCp (6, RN = CH2NMe2) reacts with 1 equiv of C6F6 to afford [1-(C6F5)-2-RNCp]FeCp (7). Complex 6 reacts with 0.5 equiv of C6F6 to afford CpFe[2-RNCp](1,4-C6F4)[2-RNCp]FeCp as a mixture of two diastereomers (meso-8, major and dl-8, minor). The relative stereochemistry of meso-8 is established by crystallographic analysis of the corresponding bis(methiodide) (12). [1-Li-2-RNCp]Fe(CpLi) (9) reacts with excess C6F6 to afford mainly the diarylated ferrocene [1-(C6F5)-2-RNCp]Fe(CpC6F5) (10). The reaction of 9 instead with 1.0 equiv of C6F6 affords a mixture of oligomeric species assigned to the formula [−(2-RNCp)FeCp(1,4-C6F4)−]n (11). In contrast to 4, 11 is sufficiently soluble for...