[(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η2-NO3)(OTf)] | 564211-86-5

• 英文名称: [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η2-NO3)(OTf)]
• 英文别名: [(C5Me5)Rh(η2-NO3)(η1-O3SCF3)]；[Rh(C5Me5)(η2-NO3)(OTf)]；[Cp*Rh(η2-NO3)(OTf)]
• CAS: 564211-86-5
• 化学式: C₁₁H₁₅F₃NO₆RhS
• 分子量: 449.21
• InChiKey: JTNVXURZNFURMV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  异硫氢酸三甲基硅酯 、 [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η2-NO3)(OTf)] 在 4-ethynyltoluene 作用下， 以 二氯甲烷 为溶剂， 生成 [(C5Me5)Rh(η1-SCN)2(HSCN)]2
  参考文献：
  名称：

  通过末端芳基炔烃的[2 + 2 + 1]环三聚反应制备新型Rhodonocenium配合物

  摘要：

  的反应的[Cp *的Rh（η 2 -NO 3）（OTF）]（1），其带有两个不稳定配体（NO 3 -和光学传递函数- ），具有末端芳基炔（苯乙炔（HC⋮CPH）或4-乙炔基甲苯（HC⋮CC 6 H ^ 4 CH 3））在醇（EtOH或ñ -BuOH），得到取代的rhodocenium阳离子的[Cp *的Rh（η 5 -C 5 H ^ 2的Ar 2 -CH（Ar）的OR）] +（OTf）-（2a - d：Ar ＝ Ph，p-甲苯基； R ＝ Et，n- Bu）。治疗1在乙醇中与4-乙炔基甲苯，接着加入伪卤化物（HSPH中，Me 3的SiN 3，或Me 3个SiNCS）在二氯甲烷也产生了取代rhodocenium阳离子的[Cp *的Rh（η 5 -C 5 H ^ 2（p -甲苯基）2 -CH（p -甲苯基）女）] +（OTF）- （女- = SPh上（图3a），N 3（图3B），NCS（3C）

  DOI：

  10.1021/om0492404
• 作为产物：
  描述：

  [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η1-NO3)(μ-Cl)]2 、 silver trifluoromethanesulfonate 以 二氯甲烷 、 丙酮 为溶剂， 以84.7%的产率得到[(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η2-NO3)(OTf)]
  参考文献：
  名称：

  NO bond cleavage and various bonding modes of the nitrato ligand in rhodium complexes: syntheses and structures of [Cp*Rh(η1-NO3)(μ-Cl)]2, {[Cp*RhCl(PPh3)(CNC6H11)]2(NO2)(NO3)}·2H2O, [Cp*Rh(η1-NO3)(η1,μ-N3)]2, [Cp*Rh(η2-NO3)(O3SCF3)], trans-{[Rh(PPh3)2(CN2,6-Me2C6H3)2](NO3)}·H2O, and {[Cp*2Rh2(η2,μ-NO2-N,O)2(η1,μ-N3)](PF6)}·0.5H2O

  摘要：

  The addition of 2 equiv. of AgNO3 to a dinuclear chloro-bridged Rh(III) compound, [Cp*RhCl2](2), resulted in the replacement of the terminal chloro ligand to give [Cp*Rh(eta(1)-NO3)(mu-Cl)](2) (1). On the other hand, the reaction of [Cp*RhCl2](2) with 4 equiv. of AgNO3 led to the formation of a mononuclear bis(nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(2)-NO3)] (2). Compound 1 reacted With PPh3 and cyclohexyl isocyanide (CN-C6H11) to give a chiral compound, {[Cp*RhCl(PPh3)(CN-C6H11)](2)(NO2)(NO3)} 2H(2)O (3.2H(2)O), which shows an unusual example of the nitrate-to-nitrite reduction in the rhodium coordination sphere. The reaction of compound 2 with either NaN3 or N3SiMe3 gave a dinuclear (eta(1)-nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(1),mu-N-3)](2) (4). On the other hand, on addition of silver triflate (AgOTf), compound 2 underwent replacement to give a monormclear (eta(2)-nitrato)-rhodium compound, [Cp*Rh(eta(2)-NO3)(OTf)] (5). In addition, compound 2 reacted with a mixture of PPh3 and 2,6-dimethylphenyl isocyanide (CN-2,6-Me2C6H3) to give trans-{[Rh(PPh3)(2)(CN-2,6-Me2C6H3)(2)](NO3)} . H2O (6. H2O), Which exhibits the complete elimination of all ligands in compound 2 and indicates the formal reduction of the rhodium metal from + 3 to + 1. The nitro-rhodium compound, {[Cp-2*Rh-2(eta(2), mu-NO2-N,O)(2)(eta(1),mu-N-3)](PF6)} . 0.5H(2)O (7 . 0.5H(2)O), was prepared by the reaction of [Cp*RhCl(dppf)](PF6) (dppf = Fe(eta(5) -C5H4PPh2)(2)) with a mixture of N3SiMe3 and AgNO3, Which also displays the N-O bond cleavage of nitrate (NO3-) to nitrite (NO2-). The structures of 1, 3 . 2H(2)O, 4, 5, 6 - HO, and 7 . 0.5H(2)O were determined by X-ray diffraction. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01466-4

文献信息

• Rhodium(III)-mediated cycloaddition of alkynes: reactivity of [Cp*Rh(η2-NO3)(OTf)] bearing two labile ligands
  作者：Won Seok Han、Soon W Lee

  DOI：10.1016/s0022-328x(03)00451-0

  日期：2003.7

  [Cp*Rh(eta(2)-NO3)(OTf)] (1) mediated cyclodimerization or cyclotrimerization of alkynes and alkynyl esters. In addition, compound I reacted with propargyl halides to give triply halide-bridged dinuclear compounds, [Cp*Rh(mu(2)-X)(3)RhCp*](OTf) (X = Cl or Br). (C) 2003 Elsevier B.V. All rights reserved.
• Reactivity of [Cp∗Rh(η6-C6H3NH2-2,6-i-Pr2)](OTf)2 toward phosphines and alkynes
  作者：Mi S. Lim、Ji Young Baeg、Soon W. Lee

  DOI：10.1016/j.jorganchem.2006.06.016

  日期：2006.9

  The cationic aniline complex [Cp*Rh(eta(6)-2,6-(Me2CH)(2)C6H3NH2)](OTf)(2) (1) was prepared from either [Cp*Rh eta(2) -NO3)(eta(1)-OTf)] or [Cp*Rh(OH2)(3)](OTf)(2) and 2,6-diisopropylaniline. Complex I underwent substitution with phosphines or phosphites, indicating the labile character of the eta(6)-aniline ligand. Complex 1 mediated cycloaddition reactions of several alkynes in refluxing ethanol: the [2 + 2] dimerization for Ph-C equivalent to C-Ph and the [2 + 2 + 1] trimerization for Ph-C equivalent to C-H and CH3C6H4-C equivalent to C-H. The unexpected cyclobutadiene complex [Cp*Rh(eta(4)-C-4(C(O)CH3)(2)H(SiMe3))] was obtained from complex 1 and MeSi-C equivalent to C-C equivalent to C-SiMe3 and structurally characterized by X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.