Rh(κ(2)-1,1,1,3,3,3-hexafluoroacetylacetonate)(C2H4)2 | 55188-59-5

• 英文名称: Rh(κ(2)-1,1,1,3,3,3-hexafluoroacetylacetonate)(C2H4)2
• CAS: 55188-59-5
• 化学式: C₉H₉F₆O₂Rh
• 分子量: 366.065
• InChiKey: CWLQDLJNAQMHER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Rh(κ(2)-1,1,1,3,3,3-hexafluoroacetylacetonate)(C2H4)2 、 三异丙基膦 以 正戊烷 为溶剂， 以91%的产率得到Rh(κ(2)-1,1,1,3,3,3-hexafluoroacetylacetonate)(C2H4)(PiPr3)
  参考文献：
  名称：

  Acetylacetonato, pentachlorophenolato and carboxylato rhodium(I) complexes and their reactivity in the C–C coupling reaction of olefins and diazoalkanes

  摘要：

  The acetylacetonato complexes [Rh(kappa(2)-O-O)(C2H4)(PiPr(3))] (O-O=acac 5, acac-f(3) 6, acac-f(6) 7) and [Rh(kappa(2)-O-O)(PiPr(3))(2)] (O-O=acac 10, acac-f(6) 11) were prepared from either [Rh(kappa(2)-O-O)(C2H4)(2)] (2-4), [Rh(eta(3)-C3H5)(PiPr(3))(2)] (8) or [RhCl(PiPr(3))(2)](2) (9) as the starting materials. While attempts to obtain the diazoalkane derivatives [Rh(kappa(2)-O-O)(N2CR2)(PiPr(3))] (R=Ph, p-Tol) failed, treatment of 5-7 with N2CC4Cl4 gave the corresponding substitution products [Rh(kappa(2)-O-O)(N2CC4Cl4)(PiPr(3))] (12-14) in good yields. The reaction of 8 with C6Cl5OH afforded the square-planar complex [Rh(kappa(2)-OC6Cl5)(PiPr(3))(2)] (15), in which the pentachlorophenolato ligand is coordinated in a chelating fashion. From 15 and C2H4, O-2 and N2CPh2 the 1:1 adducts trans-[Rh(kappa(1)-OC6Cl5)(L)(PiPr(3))(2)] (16-18) were prepared. Compound 15 catalyzes the reaction of ethene with diaryldiazomethanes to give, instead of 1, 1 -diarylcyclopropanes, the isomeric olefins R2C=CHCH3 (R = C6H5 1b, p-C6H4Me 19, p-C(6)H(4)Cl20) as the main products. The carboxylato, complexes [Rh(kappa(2)-O2CMe)(PiPr(3))(2)] (21) and [Rh(kappa(2)-O2CCF3)(PiPr(3))(2)] (25) react with N2CRR' (R = R'= C4Cl4; R=R'=Ph; R=H, Ph, R'=C(O)Ph) by opening the chelate bond to give the four-coordinate 1:1 adducts trans-[Rh(kappa(1)-O2CMe)(N2CRR')(PiPr(3))(2)] (22-24) and trans-[Rh(kappa(1)-O2CCF3)(N2CRR')(PiPr(3))(2)](26-28), respectively. Treatment of 25 with PhCHN2 produced the dinitrogen complex trans- [Rh (kappa(1)-O2CCF3)(N-2)(PiPr(3))(2)] (29). In contrast to the trifluoracetato compound 25, which catalyzes the reaction of ethene and diaryldiazomethanes N2CRR' to give mainly the trisubstituted olefins R'RC=CHCH3, the corresponding reaction of C2H4 and N2CRR' with acetato complex 21 as the catalyst affords the isomeric ethene derivatives CH2=CHCHRR' as the major products. A mechanism for this unexpected C-C coupling reaction is discussed. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.06.009
• 作为试剂：
  描述：

  (2E,5E)-hepta-2,5-dien-4-ol 在 Rh(κ(2)-1,1,1,3,3,3-hexafluoroacetylacetonate)(C2H4)2 作用下， 以 氘代苯 为溶剂， 反应 12.0h， 以15%的产率得到(2E,5E)-庚-2,5-二烯-4-酮
  参考文献：
  名称：

  1,4-二烯与2,4-戊二酸铑（I）的络合物; 配合物的热重排

  摘要：

  作为包含“跳过的”二烯片段（–CH CHCH 2 CH CH–），一系列七，2，5-二烯，七，2，5-二烯-4-醇和七，2的天然产物的模型，已经制备了5-二烯-4-醇乙酸酯。这些二烯中的一些与双（乙烯）（戊烷-2,4-去离子）铑（I）或双（乙烯）（1,1,1,5,5,5-六氟戊烷-2,4-去离子）反应铑（I）生成1：1配合物，例如[（（E，E）-庚-2,5-二烯]（1,1,1,5,5,5-六氟戊烷-2,4-去离子基）铑（我）。其他二烯，例如（Z，Z）-庚-2，5-二烯形成2∶1的络合物，其中对于每个二烯分子，一个双键与铑配位，而另一个不配位。（Z，Z）-二烯不形成1：1配合物，因为在这种配合物中每个双键的末端取代基之间将存在严重的空间相互作用。对于二烯醇和某些烯丙醇（例如丙-2-烯-1-醇）的配合物，已获得证据表明，每个OH和其最近的戊烷-2,4- CO之间存在稳定的分子内氢键。长老。当在苯中与5摩尔％的双（乙烯）（戊烷-2

  DOI：

  10.1039/dt9840000219