{rhodium(η2-acetato)(triisopropylphosphine)2} | 137854-76-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: {rhodium(η2-acetato)(triisopropylphosphine)2}
• 英文别名: [Rh(η2-O2CCH3)(P(C3H7)3)2]；[Rh(η(2)-O2CMe)(PiPr3)2]；Rh(η(2)-O2CCH3)(PiPr3)2；[Rh(κ(2)-acetato)(PiPr3)2；[Rh(κ2-acetato)(PiPr3)2]
• CAS: 137854-76-3
• 化学式: C₂₀H₄₅O₂P₂Rh
• 分子量: 482.429
• InChiKey: HESHUTJXIDWXLC-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-acetato)(triisopropylphosphine)2} 在 Na₂CO₃ 作用下， 以 乙醚 、 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  不对称双核铑（I）络合物中桥联二炔配体的空前弯曲

  摘要：

  The reaction of [Rh(eta(2)-(OCCH3)-C-2)(PiPr(3))(2)] (2) with 2 equiv of phenylbutadiyne leads, in the presence of Na2CO3, to the formation of the five -coordinate bis(diynyl)hydridorhodium(III) complex [RhH(C=CC=CPh)(2)(PiPr(3))(2)] (3) While 3 reacts with pyridine to give the stable octahedral compound [RhH(C=CC=CPh)(2)(py)(PiPr(3))(2)] (4), On treatment with carbon monoxide the square-planar complex trans-[Rh(C=CC=CPh)(CO)(PiPr(3))(2)] (6) is formed via the spectroscopically characterized 1:1 adduct 5 as a labile intermediate, Compound 6, which has also been prepared from [Rh(eta(3)-CH2C6H5)(PiPr(3))(2)] (7), CO, and phenylbutadiyne, reacts with [RhCl(PiPr(3))(2)](n) (1) to yield the binuclear complex [Rh(CO)(PiPr(3))(2)(eta(1),eta(2)-C=CC=CPh)-RhCl(PiPr(3))(2)] (8). The X-ray structural analysis of 8 (triclinic space group P1 (No, 2) with a 12.460(2) Angstrom, b = 13.954(2) Angstrom, c = 16.431(2) Angstrom, alpha = 97.98(1)degrees, beta = 91.47(1)degrees, gamma = 109.61(1)degrees, V = 2657(1) Angstrom(3), and Z = 2) reveals a square-planar coordination around each of the metal centers which are bridged by a strongly bent diynyl ligand. The reaction of 1 with phenylbutadiyne leads, via the isomeric diyne and diynyl hydride species 9 and 10 as intermediates, to the alkynyl-substituted vinylidenerhodium(I) complex trans-[RhCl-(=C=CHC=CPh)(PiPr(3))(2)] (11). In the presence of pyridine the diynyl(hydrido)rhodium derivative [RhH(C=CC=CPh)Cl(py)(PiPr(3))(2)] (12) is obtained.

  DOI：

  10.1021/om00004a035
• 作为产物：
  描述：

  Rh(η(3)-CH2C6H5)(PiPr3)2 在 CH₃COOH 作用下， 以 乙醚 为溶剂， 以81%的产率得到{rhodium(η2-acetato)(triisopropylphosphine)2}
  参考文献：
  名称：

  Werner, Helmut; Schaefer, Martin; Nuernberg, Oliver, Chemische Berichte, 1994, vol. 127, # 1, p. 27 - 38

  摘要：

  DOI：

文献信息

• Synthesis and Reactivity of Bis(ethene) Rhodium(I) and Iridium(I) Carboxylato Complexes
  作者：Helmut Werner、Sybo Poelsma、Michael E. Schneider、Bettina Windmüller、Dietmar Barth

  DOI：10.1002/cber.19961290609

  日期：1996.6

  and analogous carboxylatobis-(olefin)rhodium(I) complexes [Rh(μ-O2CR)(olefin)2]2 (4–6) were almost quantitatively prepared under heterogeneous conditions from [RhCl(C8H14)2]2 (1) or [RhCl(C2H4)2]2 (2) and CH3CO2Na · 3 H2O or RCO2H/NaOH, respectively. The X-ray crystal structure analysis of 3 confirmed the bridging position of the acetato ligands. The synthesis of [Ir(μ-O2CCH3)(C2H4)2]2 (10) was carried

  的[Rh（μ-O 2 CCH 3）（C 2 H ^ 4）2 ] 2（3）和类似carboxylatobis-（烯烃）铑（I）配合物的[Rh（μ-O 2 CR）（烯烃）2 ] 2（[4–6）几乎是在[RhCl（C 8 H 14）2 ] 2（1）或[RhCl（C 2 H 4）2 ] 2（2）和CH 3 CO 2 Na·3 H的非均相条件下定量制备的分别为2 O或RCO 2 H / NaOH。的X射线晶体结构分析3证实了乙酸根配体的桥连位置。物[Ir（μ-O的合成2 CCH 3）（C 2 H ^ 4）2 ] 2（10）用同样地进行[的IrCl（C 2 H ^ 4）2 ] 2（8）和CH 3 CO 2以Na·3 H 2 O为起始原料。所述monoethene复杂反式-的[Ir（η 1 -O 2 CCH由10和P i Pr 3获得（3）（C 2 H 4）-（P i Pr 3）2 ]（11）。它用H反
• 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-
• C–C coupling reactions in the coordination sphere of rhodium(<scp>i</scp>) and rhodium(<scp>iii</scp>): New routes for the di- and trimerization of terminal alkynes
  作者：Martin Schäfer、Justin Wolf、Helmut Werner

  DOI：10.1039/b415541f

  日期：——

  at room temperature reacts by C–C coupling to give trans-[RhClη2-(Z)-PhCCCHCHPh}(PiPr3)2] (Z)-21. The related compound trans-[RhCl(η2-HCCCHCH2)(PiPr3)2] 27, prepared from trans-[Rh(CCH)(CCH2)(PiPr3)2] 17 and HCl, rearranges to the vinylvinylidene isomer trans-[RhCl(CCHCHCH2)(PiPr3)2] 28. While stepwise reaction of 2 with CF3CO2H yields, via alkynyl(vinyl)rhodium(III) intermediates (Z)-29 and (E)-29

  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
• Allylrhodium complexes [Rh(η³-2-RC₃H₄)(PPrⁱ₃)₂] as precursors for carboxylato, alkynyl(hydrido), alkynyl(ethene) and alkynyl(vinylidene) rhodium derivatives
  作者：Martin Schäfer、Justin Wolf、Helmut Werner

  DOI：10.1039/c39910001341

  日期：——

  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.
• 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.