[RhCl2(CD2Cl)(2,6-(C(H)=N-i-Pr)2C5H3N)] | 185117-12-8

• 英文名称: [RhCl2(CD2Cl)(2,6-(C(H)=N-i-Pr)2C5H3N)]
• 英文别名: [RhCl2(CD2Cl)(2,6-(CHN(i-Pr))2C5H3N)]
• CAS: 185117-12-8
• 化学式: C₁₄H₂₁Cl₃N₃Rh
• 分子量: 442.589
• InChiKey: XICHKPNNZOEQDE-MUYKIMIDSA-L

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

• 作为产物：
  描述：

  [Rh(OPh)(2,6-(CHN(i-Pr))2C5H3N)] 以 二氯甲烷-D2 、 甲苯 为溶剂， 生成 [RhCl2(CD2Cl)(2,6-(C(H)=N-i-Pr)2C5H3N)]
  参考文献：
  名称：

  芳氧基铑配合物，含有叔氮配体，CO键形成，与苯酚的氢键结合和氧化加成反应。Rh（III）-乙酰基配合物的分子结构

  摘要：

  摘要含有强电子给体NN'-的新型苯酚铑（I）络合物[Rh（OPh）（2,6-（CH = R2）2C5H3N）]（R2 = i-Pr（3），t-Bu（4））通过[RhCl（2,6-（CH = R2）2C5H3N）]（R2 = i-Pr（1），t-Bu（2））与NaOPh的复分解反应制备了N个配体。这些苯酚铑（I）配合物3和4对O2非常敏感，但对H2O稳定，它们与苯酚生成加合物[Rh（OPh）（2,6-（CH = NR2）2C5H3N）]·HOPh（R2 = i-Pr（5），t-Bu（6）），其中包含强OH = O氢键。氢键合的酚不能用二乙醚萃取，而在NMR时间尺度上没有观察到氢键合的酚和酚盐配体在4中的交换。但是，少量过量的苯酚会导致氢键合的苯酚，配位的酚盐配体和游离苯酚在NMR时间尺度上发生交换。3和4与对硝基苯酚反应制得[Rh（OC6H4-（NO2-4））（2,6-（CH = R2）2C5H3N）]·HOPh（R2

  DOI：

  10.1016/s0020-1693(97)05821-0

文献信息

• Reactions of [RhCl(diene)]₂ with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes
  作者：Hendrikus F. Haarman、Frank R. Bregman、Jan-Meine Ernsting、Nora Veldman、Anthony L. Spek、Kees Vrieze

  DOI：10.1021/om960760b

  日期：1997.1.1

  Reaction of [RhCl(diene)](2) (diene = 1,5-cyclooctadiene (COD) or bicyclo[2.2.1] hepta-2,5-diene (NBD)) with the N-N-N nitrogen ligands 2,6-(C(R(1))=N-R(2))(2)C5H3N in CD(2)CL(2) or CH2Cl2 yielded the five-coordinate complexes [RhCl(2,6-(C(H)=N-R(2))(2)C5H3N)(diene)] (diene = NBD; R(2) = i-Pr, t-Bu, and p-anisyl), which has been isolated for NBD but not for COD. A single-crystal X-ray determination showed that [RhCl(2,6-(C(H)=N-p-anisyl)(2)C5H3N)(NBD)] has a distorted trigonal bipyramidal configuration with the pyridyl N-atom, one imine N-atom, and one alkene double bond in the equatorial plane, while the second alkene bond and the chloride atom occupy the axial positions. This conformation containing one noncoordinated imine moiety is clearly retained at 183 K in CD2Cl2, as is also the case for the other complexes. For the COD complexes, the reaction is more complicated, as the intermediates that are observed depend on the substituents R(1) and R(2) of the N-N-N nitrogen ligand. The five-coordinate complexes [RhCl(2,6-(C(R(1))=N-R(2))(2)C5H3N)(COD)] could be observed at low temperatures for R(1) = H and R(2) = i-Pr, t-Bu, and p-anisyl, while for R(1) = Me and R(2) = p-anisyl, this intermediate could not be observed; instead, [Rh(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)(2)]Cl-+(-) was found, which shows the presence of one N-N-N Ligand bonded as a bidentate ligand and one N-N-N Ligand bonded as a terdentate ligand at low temperatures. Further reaction of [Rh(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)(2)]Cl-+(-) with [RhCl(COD)](2) afforded [RhCl(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)] and subsequently, via oxidative addition of CD2Cl2, the complex [RhCl2(CD2Cl)(2,6-(C(Me)=N-p-anisyl)(2)C5H3N)]. The dynamic properties of the five-coordinate diene complexes [RhCl(2-(C(H)=N-R(2))-6-(Me)C5H3N)(NBD)] (R(2) = i-Pr, t-Bu, and p-anisyl), which contain N-N nitrogen Ligands, and of the new complexes [Rh(2-(C(H)=N-R(2))-6-(Me)C5H3N)(NBD)]OTf (R(2) i-Pr, t-Bu, and p-anisyl) and of [Rh(2,2'-bipyrimidine)(NBD)]OTf have been investigated. A single-crystal X-ray determination of [RhCl(2-(C(H)=N-i-Pr)-6-(Me)C5H3N)(NBD)] showed structural features which are analogous to those of RhCl(2,6-(C(H)=N-p-anisyl)(2)C5H3N)(NBD)].