trans-[Rh(κ(1)-trifluoroacetato)(PiPr3)2N2 | 819082-52-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-[Rh(κ(1)-trifluoroacetato)(PiPr3)2N2
• CAS: 819082-52-5
• 化学式: C₂₀H₄₂F₃N₂O₂P₂Rh
• 分子量: 564.414
• InChiKey: QVQVYMWKABUUIG-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  {rhodium(η2-trifluoracetato)(triisopropylphosphine)2} 、 二苯基重氮甲烷 以 正戊烷 为溶剂， 以59%的产率得到trans-[Rh(κ(1)-trifluoroacetato)(PiPr3)2N2
  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