bis(1,2-bis(diphenylphosphino)ethane)rhodium(I) | 47895-57-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(1,2-bis(diphenylphosphino)ethane)rhodium(I)
• 英文别名: {Rh(1,2-bis(diphenylphosphino)ethane)2}(1+)；[Rh(1,2-bis(diphenylphosphino)ethane)2](1+)；[Rh(dppe)2](1+)
• CAS: 47895-57-8
• 化学式: C₅₂H₄₈P₄Rh
• 分子量: 899.754
• InChiKey: BCQRMZOQCAWENS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  57.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  bis(1,2-bis(diphenylphosphino)ethane)rhodium(I) 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Electrochemistry of coordination compounds

  摘要：

  DOI：

  10.1016/s0022-0728(73)80059-2
• 作为产物：
  描述：

  [HRh(dppe)2(acetonitrile)][BF4]2*CH3CN 在 4-bromoaniline 作用下， 以 乙腈 为溶剂， 生成 bis(1,2-bis(diphenylphosphino)ethane)rhodium(I)
  参考文献：
  名称：

  HRh(dppb)₂, a Powerful Hydride Donor

  摘要：

  The Rh(I) and Rh(III) hydrides HRh(dppb)(2) and [HRh(dppb)(2)(NCCH3)](BF4)(2) (where dppb is 1,2-(bis(diphenylphosphino)benzene) have been prepared, and a structural study of [HRh(dppb)2(NCCH3)](BF4)2 has been completed. The latter complex is an octahedral complex with a trans arrangement of the hydride and acetonitrile ligands. A pK(a) value of 9.4 was measured for this complex by equilibration of [Rh(dppb)(2)](BF4) with 4-bromoanilinium tetrafluoroborate in acetonitrile. [Rh(dppb)21(BF4) reacts with H-2 in the presence of Pt(dmpp)(2), which acts as a base, to form HRh(dppb)(2) and [HPt(dmpp)(2)](BF4) (where dmpp = 1,2-bis-(dimethylphosphino)propane). An equilibrium constant of 0.42 +/- 0.2 was measured for this reaction. Using this equilibrium measurement and a thermodynamic cycle, the hydride donor ability (DeltaGdegrees(H-)) of HRh(dppb)2 was determined to be 34 kcal/mol. This value indicates that HRh(diphosphine)(2) complexes are powerful hydride donors. Similarly the pKa value of HRh(dppb)2 was calculated to be 35 from a thermodynamic cycle that included the potential of the Rh(I/-I) couple (E-1/2 = -2.02 V vs ferrocene). These results combined with results from the literature suggest the following order of hydricity for five-coordinate, 18-electron hydrides: second row > third row > first row. Similarly an acidity order of second row first row > third row is deduced.

  DOI：

  10.1021/om020421k
• 作为试剂：
  描述：

  环己烷 在 bis(1,2-bis(diphenylphosphino)ethane)rhodium(I) 四丁基高氯酸铵 作用下， 以 苯甲腈 为溶剂， 生成 环已基环已烷 、 环己烯
  参考文献：
  名称：

  Activation of carbon-hydrogen bonds by [Rh(diphos)2]0

  摘要：

  DOI：

  10.1021/ja00523a043

文献信息

• Enthalpy changes in oxidative addition reactions of iodine with monomeric and dimeric rhodium(I) complexes
  作者：J.U. Mondal、K.G. Young、D.M. Blake

  DOI：10.1016/s0022-328x(00)85147-5

  日期：1982.12

  The heat of reaction for addition of iodine to the planar complexes RhCl(CO)dppe, Rh(dppen)2+, Rh(dppe)2+ and to the dimer Rh2Cl2(CO)2(dppm)2 has been obtained by a calorimetric method. Iodine forms stronger RhI bonds with RhCl(CO)dppe than with the bichelate complexes. The presence of metal-metal interaction in the iodine addition compound of Rh2Cl2(CO)2(dppm)2 makes a significant contribution to

  获得了将碘添加到平面络合物RhCl（CO）dppe，Rh（dppen）2 +，Rh（dppe）2 +以及二聚体Rh 2 Cl 2（CO）2（dppm）2上的反应热。通过量热法。碘与RhCl（CO）dppe形成的Rh bondsI键比双螯合物形成的RhI键更强。Rh 2 Cl 2（CO）2（dppm）2的碘加成化合物中金属与金属的相互作用对氧化加成的焓变具有重要作用。在IR和31的基础上讨论了配合物的立体化学。1 H NMR谱。
• Reversible Opening of the Triangular Structure of a Sulfido-Bridged ZrRh₂ Early−Late Heterobimetallic Complex Induced by Bis-(diphenylphosphino)methane
  作者：Marc A. F. Hernandez-Gruel、Fernando J. Lahoz、Isabel T. Dobrinovich、F. Javier Modrego、Luis A. Oro、Jesús J. Pérez-Torrente

  DOI：10.1021/om061092p

  日期：2007.5.1

  Reaction of the early−late heterobimetallic complexes [Cptt2Zr(μ3-S)2M(CO)}2(μ-dppm)] (M = Rh, Ir) with dppm (bis-(diphenylphosphino)methane) yields the compounds [Cptt2Zr(μ-S)2M(μ-CO)2(μ-dppm)M(η2-dppm)] (M = Rh (3), Ir (4)). The molecular structure of 3 shows a bent trimetallic ZrRhRh chain with tetrahedral, trigonal-bipyramidal, and square-pyramidal geometries, respectively. This trinuclear compound

  早-晚双核配合物的反应的[Cp TT 2的Zr（μ 3 -S）2 M（CO）} 2（μ-DPPM）]（M =铑，铱）与DPPM（双- （二苯基膦基）甲烷）产率的化合物的[Cp TT 2的Zr（μ-S）2 M（μ-CO）2（μ-DPPM）M（η 2 -DPPM）]（M =的Rh（3），IR（4））。3的分子结构分别显示了弯曲的三金属ZrRhRh链，分别具有四面体，三角双锥体和方形锥体的几何形状。这种三核化合物显示出价态的Rh（II）-Rh（0）金属-金属键合单元，其是由于金属配体[Cp TT 2 Zr（S）2 ] 2-的不寻常螯合配位而形成的，并通过存在两个不对称的桥接羰基配体，它们与不饱和Rh（II）金属相互作用。形成3是可逆的，并且平衡1 + DPPM⇆ 3（在溶液中已经观察到ķ ≈16在22℃下用C 6 d 6）。三角形芯在heterotrimetallic化合物开口的[Cp TT 2的Zr（μ
• Heterobinuclear IrRh, RuRh and Rulr complexes with pyrazolate bridging ligands: reactivity towards chelating diphosphines; crystal structure of [(C₅Me₅)Ir(µ-pz)₂(µ-CO)-Ir(CO)(dppen)]BPh₄·0.5MeOH [pz = pyrazolate, dppen =cis-1,2-bis(diphenylphosphino)ethylene]
  作者：Daniel Carmona、Joaquina Ferrer、Fernando J. Lahoz、Luis A. Oro、Josefa Reyes、Montserrat Esteban

  DOI：10.1039/dt9910002811

  日期：——

  intermediates [LM(µ-pz)2(µ-CO)M′(CO)(L–L)]A have been isolated in some cases. The crystal structure of one of these [(C5Me5)Ir(µ-pz)2(µ-CO)Ir(CO)(dppen)] BPh4·0.5MeOH 19 has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P21/c, a= 15.996(2), b= 22.199(4), c= 18.874(3)Å, β= 115.04(1)° and Z= 4. The complex cation consists of two iridium atoms bridged by two pyrazolates and

  通式[LClM（µ-PZ）2 M'（cod）]的配合物1 – 5 [L = C 5 Me 5，M = Rh或Ir; L =对-cymene，Me = Ru；M'= Rh或Ir; PZ =吡唑酸酯；cod =环辛基-T，5-二烯（并非所有可能的组合）]和[（MEC 6 H 4 Pr i - p）Ru（µ-PZ）（µ-Cl）2 Rh（cod）] 7的制备从单核乙酰丙酮化物和吡唑或含吡唑化物的部分。配合物1 - 5与CO产生衍生物[LClM（μ-PZ）反应2 M'（CO）2 ] 8– 12。配合物[（C 5我5）ClRh（μ-PZ）2的Rh（CO）2 ] 13和[（MEC 6 ħ 4镨我- p）CIRu（μ-PZ）2的Ir（CO）2 ] 12与反应的NaX，得到[（C 5我5）XRH（μ-PZ）2的Rh（CO）2 ]（X = I，14 ;或N 3，15）和[（MEC 6 ħ 4镨我- p）[图形省略]
• The Anions [Cp^tt₂Zr(μ-S)₂M(CO)₂]^- (M = Rh, Ir) as Versatile Precursors for the Synthesis of Sulfido-Bridged Early−Late Heterotrimetallic (ELHT) Compounds
  作者：Marc A. F. Hernandez-Gruel、Isabel T. Dobrinovitch、Fernando J. Lahoz、Luis A. Oro、Jesús J. Pérez-Torrente

  DOI：10.1021/om700749n

  日期：2007.12.1

  intermediate heterotrinuclear compound [Cptt2Zr(μ3-S)2Rh(dppe)}Rh(CO)2}] (4). Reaction of the heterodinuclear anion [Cptt2Zr(μ-S)2Ir(CO)2]-, generated in situ, with [Rh(μ-Cl)(cod)]2, [RhCl2(CO)2]- and [Pd(μ-Cl)(η3-C3H5)]2 affords the d0−d8−d8 early−late compounds [Cptt2Zr(μ3-S)2Ir(CO)2}Rh(cod)}] (6), [Cptt2Zr(μ3-S)2Ir(CO)2}Rh(CO)2}] (7), and [Cptt2Zr(μ3-S)2Ir(CO)2}Pd(η3-C3H5)}] (8) each with a symmetrical

  [CP的反应TT 2的Zr（μ 3 -S）2 的Ir（CO）2 } 2 ]（CP TT =η 5 -1,3-二-叔丁基环戊二烯基）配有DPPE（1,2-双- （二苯基膦基）乙烷）提供离子对化合物[Ir（CO）（DPPE）2 ] [CP TT 2 Zr（μ-S）2 Ir（CO）2 ]（2）。相关化合物[Rh（DPPE）2 ] [CP TT 2 Zr（μ-S）2 Rh（CO）2 ]（5）已经在溶液中通过下述物质反应得到的一氧化碳气氛下的[CP TT 2的Zr（μ 3 -S）2 的Rh（CO）2 } 2 ]与通过中间异三化合物DPPE的[CP TT 2的Zr（μ 3 -S）2 Rh（DPPE）} Rh（CO）2 }]（4）。原位产生的异双核阴离子[CP TT 2 Zr（μ-S）2 Ir（CO）2 ] -与[Rh（μ-Cl）（cod）] 2，[RhCl 2（CO）2 ]反应-和[钯（μ-Cl）的（η
• Pilloni, Giuseppe; Zotti, Gianni; Martelli, Mario, Inorganic Chemistry, 1982, vol. 21, # 3, p. 1283 - 1284
  作者：Pilloni, Giuseppe、Zotti, Gianni、Martelli, Mario

  DOI：——

  日期：——