bis(1,4-bis(diphenylphosphino)butane)rhodium(I) tetrafluoroborate | 70196-23-5

• 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(1,4-bis(diphenylphosphino)butane)rhodium(I) tetrafluoroborate
• CAS: 70196-23-5
• 化学式: BF₄*C₅₆H₅₆P₄Rh
• 分子量: 1042.67
• InChiKey: VDBGHBYKRKZMSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.36
• 重原子数：
  66.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.14
• 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(1,4-bis(diphenylphosphino)butane)rhodium(I) tetrafluoroborate 在 H₂ 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  James, Brian R.; Mahajan, Devinder, Canadian Journal of Chemistry, 1980, vol. 58, p. 996 - 1004

  摘要：

  DOI：
• 作为产物：
  描述：

  、 silver tetrafluoroborate 以 二氯甲烷 为溶剂， 生成 bis(1,4-bis(diphenylphosphino)butane)rhodium(I) tetrafluoroborate
  参考文献：
  名称：

  James, B. R.; Mahajan, D., Canadian Journal of Chemistry, 1979, vol. 57, p. 180 - 187

  摘要：

  DOI：

文献信息

• Cationic complexes of rhodium(I) as catalysts in the homogeneous O2-oxidation of terminal alkenes to methyl ketones
  作者：Mario Bressan、Franco Morandini、Antonino Morvillo、Pierluigi Rigo

  DOI：10.1016/0022-328x(85)87071-6

  日期：1985.1

  [Rh(LL)2]+, [Rh(LL)(diene)]+ and [Rh(LL)S2]+ complexes are effective as catalysts for the oxidation by dioxygen of terminal olefins to methyl ketones. The complexes act as monooxygenases, the second oxygen atom being transferred to the alcohol solvent.

  [Rh（LL）2 ] +，[Rh（LL）（二烯）] +和[Rh（LL）S 2 ] +络合物有效地用作末端烯烃的双氧氧化为甲基酮的催化剂。络合物起单加氧酶的作用，第二个氧原子被转移到醇溶剂中。
• Carbonyl adducts of bis(1,4-bis(diphenylphosphino)butane)rhodium(I) cation. Crystal and molecular structure of [Rh2(Ph2P(CH2)4PPh2)3(CO)4](PF6)2
  作者：L.H. Pignolet、D.H. Doughty、S.C. Nowicki、M.P. Anderson、A.L. Casalnuovo

  DOI：10.1016/s0022-328x(00)90518-7

  日期：1980.12

  of [Rh(dppb)2]+X−, where X = BF4 or PF6 and dppb = Ph2P(CH2)4PPh2, yields the binuclear complex [Rh2(dppb)3(CO)4]2+ and uncoordinated dppb. This complex was isolated in the solid state as the PF6 salt and characterized by single crystal X-ray diffraction. The structure consists of two trigonal bipyramidal RhP3(CO)2 cores bridged by a dppb ligand via axial coordination sites. The CO ligands are cis and

  CO与CH反应2氯2个的[Rh（DPPB）的解决方案2 ] + X - ，其中X = BF 4或PF 6和DPPB =苯基2 P（CH 2）4 PPH 2，得到的双核配合物的[Rh 2（DPPB）3（CO）4 ] 2+和未配位的DPPB。该固体以PF 6盐的形式分离出来，并通过单晶X射线衍射表征。该结构由两个三角双锥体RhP 3（CO）2组成核心由DPPB配体通过轴向配位点桥接。CO配体是顺式且占据赤道位点，而螯合的DPPB配体跨越它们各自配位核的赤道和轴向位点。在P晶胞中包含一个双核分子（Rh 2（DPPB）3）（CO）4 ]（PF 6）2，使得反向中心存在于桥接DPPB配体的骨架的中心。晶胞尺寸为a = 12.385（2），b = 15.286（2），c = 12.353（4）Å，α= 99.77（2），β= 107.03（2），γ= 103.66（1）°和V = 2100埃3。使用总
• Interconversion between Zwitterionic and Cationic Rhodium(I) Complexes of Demonstrated Value as Catalysts in Hydroformylation, Silylformylation, and Hydrogenation Reactions. Dynamic ³¹P{¹H} NMR Studies of (η⁶-PhBPh₃)^-Rh⁺(DPPB) and [Rh(DPPB)₂]⁺BPh₄^- in Solution
  作者：Zhongxin Zhou、Glenn Facey、Brian R. James、Howard Alper

  DOI：10.1021/om960112s

  日期：1996.5.14

  Treatment of an orange solution of [Rh(COD)(DPPB)](BF4-)-B-+ (2) in MeOH with 2 equiv of NaBPh(4) at room temperature (RT) afforded an orange precipitate, [Rh(COD)(DPPB)](+)BPh(4)(-) (3), in 94% yield. Reaction of the cationic rhodium complex 3 with Hp under ambient conditions in CH2Cl2 for Ih gave the zwitterionic complex (eta(6)-PhBPh(3))-Rh+(DPPB) (4) in quantitative yield. Although 3 is stable in the solid state, it has the propensity in solution to convert to the zwitterionic complexes (eta(6)-PhBPh(3))Rh--(+)(COD) (1) and (eta(6)-PhBPh(3))Rh--(+)(DPPB) (4) along with a small amount of [Rh-x(DPPB)(2x)](x+)[BPh(4)(-)](x). Addition of 1, 2, and 4 equiv of DPPB to the CD2Cl2 solution of (eta(6)-PhBPh(3))Rh--(+)(NBD) (6) under N-2 resulted in the formation of [Rh(NBD)(DPPB)](+)BPh(4)(-) (7) and [Rh(DPPB)(2)](+)BPh(4)(-) (5) in ratios of 90/10, 57/43, and 0/100, respectively, while addition of 2 equiv of DPPB to the CD2Cl2 solution of 6, under an atmosphere of H-2 at RT, gave 4 and 5 in an ratio of 35/65. ''Slowed'' eta(6)-PhBPh(3)(-) rotation about the (eta(6)-PhBPh(3))(-)-Rh bond axis in (eta(6)-PhBPh(3))Rh--(+)(DPPB) (4) was established by a variable-temperature P-31H-1} NMR study. Variable-temperature (31)p(H-1) NMR spectra of [Rh(DPPB)(2)](+)BPh(4)(-) (5) along with the low-temperature P-31H-1} COSY and EXSY NMR spectra demonstrated the presence of an equilibrium between [Rh(DPPB)(2)](+) (5 alpha) and [Rh(DPPB)(mu-DPPB)](2+)(2) (5 beta).
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Rh: SVol.B3, 4.26.2.9, page 182 - 183
  作者：

  DOI：——

  日期：——