{rhodium(η2-trifluoracetato)(triisopropylphosphine)2} | 137854-77-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: {rhodium(η2-trifluoracetato)(triisopropylphosphine)2}
• 英文别名: [Rh(η2-O2CCF3)(P(C3H7)3)2]；[Rh(κ(2)-trifluoroacetato)(PiPr3)2；[Rh(κ2-trifluoroacetato)(PiPr3)2]
• CAS: 137854-77-4
• 化学式: C₂₀H₄₂F₃O₂P₂Rh
• 分子量: 536.401
• InChiKey: FSUUNEYGBNFXGY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  {rhodium(η2-trifluoracetato)(triisopropylphosphine)2} 、 (E)-1,4-Diphenylbut-1-en-3-yne 以 乙醚 为溶剂， 以89%的产率得到trans-[Rh(κ1-trifluoroacetato)(η2-(E)-PhC2CH=CHPh)(PiPr3)2]
  参考文献：
  名称：

  铑（I）和铑（III）的配位领域中的CC偶联反应：末端炔烃二聚和三聚的新途径

  摘要：

  炔基（亚乙烯基）铑（I）配合物反式-[Rh（C CR）（C CHR）（P i Pr 3）2 ] ，5、6通过迁移插入与CO反应生成立体选择性的丁烯基化合物反式-[[铑{η 1 - （ż）-C（CHR）C CR}（CO）（P我镨3）2 ]（ż） - 7-9，其中（的ž） - 7 （R =苯基）和（ž）-8 （R = tBu）在加热或紫外线照射下会重新排列为（E）异构体。类似地，反式- [铑{η 1 -C（CH 2）C器CPh}（CO）（P我镨3）2 ] 12和反式- [铑{η 1 - （ż）-C（CHCO 2我）C制备了CR}（CO）（P i Pr 3）2 ]（Z）-15，（Z）-16。在室温下，相应的“未取代”衍生物反过来- [铑{η 1 -C（CH 2）C CH}（CO）（P我镨3）2 ] 18处于平衡状态与异构体丁三烯反式- [铑（η 1 -CH Ç Ç CH 2）（CO ）（P i Pr

  DOI：

  10.1039/b415541f
• 作为产物：
  描述：

  {rhodium(hydrido)(η3-2-MeC3H4)(η1-trifluoracetato)(triisopropylphosphine)2} 以 苯 为溶剂， 以80%的产率得到{rhodium(η2-trifluoracetato)(triisopropylphosphine)2}
  参考文献：
  名称：

  Allylrhodium complexes [Rh(η³-2-RC₃H₄)(PPrⁱ₃)₂] as precursors for carboxylato, alkynyl(hydrido), alkynyl(ethene) and alkynyl(vinylidene) rhodium derivatives

  摘要：

  Allylrhodium complexes [Rh(eta-3-2-RC3H4(PPri3)2,]2,3, which are prepared from [RhCl(PPri3)2]n 1 and allyl Grignard reagents, react with R'CO2H (R' = Me, CF3) to give [Rh(eta-2-O2CR')(PPri3)2] 4,5 but with alk-1-ynes RC = CH (R = C6H5, Me, H) to give the alkynyl(vinylidene) compounds trans-[Rh(C = CR)(= C = CHR)(PPri3)2] 8-10; in the presence of pyridine (py) the octahedral bis(alkynyl)hydrido derivatives [RhH(C = CR)2(py)(PPri3)2] 11-13 are obtained.

  DOI：

  10.1039/c39910001341

文献信息

• Vinyliden-Übergangsmetallkomplexe XXX. Reaktionen von acetato- und trifluoracetato-rhodium(I)-komplexesn mit 1-alkinen: Ein beispiel für die balance zwischen isomeren π-alkin-alkinyl(hydrido)- und vinyliden-metallverbindungen
  作者：Martin Schäfer、Justin Wolf、Helmut Werner

  DOI：10.1016/0022-328x(94)24750-d

  日期：1995.1

  heating, both types of complexes, trans-[Rh(η1-O2CCF3)(HC≡CR)(PiPr3)2] (6–8) and [RhH(C≡CR)(η2-O2CCF3)(PiPr3)2] (9,10), rearrange to give the isomeric vinylidene-rhodium(I) compounds trans-[Rh(η1-O2CCF3)(CCHR)(PiPr3)2] (11–14). Analogous acetatorhodium(I) and -rhodium(III) complexes, trans-[Rh(η1-O2CCH3)(HC≡CR)(PiPr3)2] (16,17), [RhH(C≡CR)(η2-O2CCH3)(PiPr3)2] (18,19) and trans-[Rh(η1-O2CCH3)(CCHR)(PiPr3)2]

  铑配合物的[Rh（η 2 -O 2 CCF 3）（PiPr 3）2 ]（2）反应与1-炔在-20℃下在戊烷中，得到任一四坐标alkynerhodium（I）或六配位的炔（氢化）铑（III）衍生物。在加热时，这两种类型的复合物，反式- [铑（η 1 -O 2 CCF 3）（HC≡CR）（PiPr 3）2 ]（6-8）和[RhH的（C≡CR）（η 2 -O 2 CCF 3）（PiPr 3）2 ]（9,10），重新排列，得到同分异构的亚乙烯基-铑（I）的化合物，反式- [铑（η 1 -O 2 CCF 3）（CCHR）（PiPr 3）2 ]（11-14）。类似acetatorhodium（I）和-铑（III）络合物，反式- [铑（η 1 -O 2 CCH 3）（HC≡CR）（PiPr 3）2 ]（16,17），[RhH的（C≡CR） （η 2 -O 2 CCH 3）（PiPr 3）2 ]（18,19）和反式-
• Acetylacetonato, pentachlorophenolato and carboxylato rhodium(I) complexes and their reactivity in the C–C coupling reaction of olefins and diazoalkanes
  作者：Helmut Werner、Norbert Mahr、Michael E. Schneider、Marco Bosch、Justin Wolf

  DOI：10.1016/j.poly.2004.06.009

  日期：2004.11

  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.
• Werner, Helmut; Schaefer, Martin; Nuernberg, Oliver, Chemische Berichte, 1994, vol. 127, # 1, p. 27 - 38
  作者：Werner, Helmut、Schaefer, Martin、Nuernberg, Oliver、Wolf, Justin

  DOI：——

  日期：——