Fluorous biphasic catalysis:: Synthesis and characterization of copper(I) and copper(II) fluoroponytailed 1,4,7-Rf-TACN and 2,2′-Rf-bipyridine complexes -: Their catalytic activity in the oxidation of hydrocarbons, olefins, and alcohols, including mechanistic implications
Fluorous biphasic catalysis:: Synthesis and characterization of copper(I) and copper(II) fluoroponytailed 1,4,7-Rf-TACN and 2,2′-Rf-bipyridine complexes -: Their catalytic activity in the oxidation of hydrocarbons, olefins, and alcohols, including mechanistic implications
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DOI：
10.1002/chem.200304771
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发表时间：
2003-09-05
影响因子：
4.3
通讯作者：
Fish, RH
中科院分区：
文献类型：
--
作者：
Contel, M;Izuel, C;Fish, RH
在这篇关于氟双相催化 (FBC) 的文章中，我们介绍了新型铜配合物的合成和表征，并定义了它们作为预催化剂在烃类、烯烃和醇的 FBC 氧化中的作用。因此，之前报道的但特征很少的氟马尾配体 2,2'-R-f-联吡啶 (R-f = (CH2)(3)C8F17) 2 以及新的 Cull 氟马尾羧酸合成子复合物 [Cu(C8F17(CH2)(2)CO2)(2)] 3 将得到解决。此外，前述配体 1,4,7-R-f-TACN 1 或 2,2'-Rf-联吡啶 2 与 3 的反应提供了新的全氟庚烷可溶性 Cu-II 配合物，[Cu(C8F17(CH2)(2)CO2)(2)(R-f-tacn)] 4 和[Cu(C8F17(CH2)(2)CO2)(2)(R-f-bpy)]分别为5。 I 与 [Cu(CH3CN)(4)]PF6 或 [CuCl] 的反应提供了新的 Cu-I 配合物，可以将其分离并完全表征为 [Cu(R-f-tacn)X']X，其中 X = PF6 (6) 或 V' = Cl (7)（溶于全氟庚烷）。通过元素分析、质谱、红外、漫反射紫外/可见和 EPR 光谱对剔除和切割复合物 4-7 进行了表征；配合物 7 还通过 H-1 和 F-19{H-1} NMR 光谱进行了表征。配合物 4 和 5 以及原位生成的 6 和 7 作为烃和烯烃官能化的预催化剂进行了评估。这些底物在必要的氧化剂叔丁基氢过氧化物 (TBHP) 和氧气存在下，在 FBC 条件下进行 5、7 和 Cu-I 盐与 2 的氧化反应。然而，由于配体显着解离，与配体 2 的配合物无法回收。 Cull配合物4与配体1在90℃单相FBC条件下，用TEMPO（2,2,6,6-四甲基哌啶基-1-氧基）和02将4-硝基苯甲醇氧化成4-硝基苯甲醛；预催化剂4可用于另外四个催化循环而不会损失活性。我们将讨论有关这些 FBC 氧化反应的合理机制。
In this contribution on fluorous biphasic catalysis (FBC), we present the synthesis and characterization of new copper complexes, and define their role, as precatalysts, in the FBC oxidation of hydrocarbons, olefins, and alcohols. Thus the previously reported, but poorly characterized, fluoroponytailed ligand, 2,2'-R-f-bipyridine (R-f = (CH2)(3)C8F17) 2, as well as the new Cull fluoroponytailed carboxylate synthon complex [Cu(C8F17(CH2)(2)CO2)(2)] 3, will be addressed. Moreover, the reaction of previously described ligands, 1,4,7-R-f-TACN 1, or 2,2'-Rf-bipyridine 2 with 3 afforded new perfluoroheptane-soluble Cu-II complexes, [Cu(C8F17(CH2)(2)CO2)(2)(R-f-tacn)] 4 and [Cu(C8F17(CH2)(2)CO2)(2)(R-f-bpy)] 5, respectively. The reaction of I with [Cu(CH3CN)(4)]PF6 or [CuCl] provided new Cu-I complexes, which could be isolated and fully characterized as [Cu(R-f-tacn)X']X, in which X = PF6 (6) or V' = Cl (7) (soluble in perfluoroheptane). The Cull and Cut complexes, 4-7, were characterized by elemental analysis, mass spectrometry, and IR, diffuse reflectance UV/Vis, and EPR spectroscopies; complex 7 was also characterized by H-1 and F-19{H-1} NMR spectroscopy. Complexes 4 and 5, as well as 6 and 7 generated in situ, were evaluated as precatalysts for hydrocarbon and olefin functionalization. The oxidation reactions of these substrates in the presence of the necessary oxidants, tert-butyl hydroperoxide (TBHP) and oxygen gas, proceeded under FBC conditions for 5, 7, and Cu-I salts with 2. However, the complexes with ligand 2 could not be recycled, owing to significant ligand dissociation. The Cull complex 4, with the ligand 1, provide the oxidation of 4-nitrobenzyl alcohol to 4-nitrobenzaldehyde under single-phase FBC conditions at 90degreesC with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy) and 02; the precatalyst 4, can be utilized for an additional four catalytic cycles without loss of activity. Plausible mechanisms concerning these FBC oxidation reactions will be discussed.