[Ru(η(5)-C5H5)(η(4)-C5H4O)(pyridine)](CF3SO3) | 181654-26-2

• 英文名称: [Ru(η(5)-C5H5)(η(4)-C5H4O)(pyridine)](CF3SO3)
• 英文别名: [Ru(η(5)-C5H5)(η(4)-C5H4O)(pyridine)]OSO2CF3；[Ru(η(5)-C5H5)(η(4)-C5H4O)(pyridine)]CF3SO3
• CAS: 181654-26-2
• 化学式: CF₃O₃S*C₁₅H₁₄NORu
• 分子量: 474.423
• InChiKey: SUWWEXRAZOWLAB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  [Ru(η(5)-C5H5)(η(4)-C5H4O)(pyridine)](CF3SO3) 、 三环己基膦 以 硝基甲烷 为溶剂， 以82.3%的产率得到[Ru(η(5)-C5H5)(η(5)-C5H3OH-2-PCy3)]CF3SO3
  参考文献：
  名称：

  Kinetics and Mechanism of Nucleophilic Substitutions on Coordinated Polyenes and Polyenyls. 1. Reactions of Tertiary Phosphines with [Ru(η⁵-C₅H₅)(η⁴-C₅H₄O)(L)]CF₃SO₃ (L = CH₃CN, Benzonitrile, Thiourea, Pyridine)

  摘要：

  Complexes of the type [Ru(eta(5)-C5H5)(eta(4)-C5H4O)(L)]CF3SO3 (L = CH3CN (1a), benzonitrile (1b), pyridine (2), thiourea (3)) react with tertiary phosphines to give either 1,1'- or 1,2-disubstituted ruthenocenes depending on the basicity of the entering phosphine and the nature of L. For 1a and 1b, only phosphines with a pK(a) value above 5 substitute on the C5H5 ring while others substitute on the C5H4O ring. For compounds 2 and 3, the two rings are deactivated such that only the most basic phosphines react, and they attack only the C5H4O ring. In some cases of the reactions of 2 and 3, an intermediate is observed in which the monodentate ligand has migrated to the C5H5 ring while the entering nucleophile coordinates to the metal center. The mechanism by which phosphines attack a coordinated C5H4O ring has been established, and detailed kinetic parameters have been obtained. For the reaction of 1a with PPh(3), PPh(2)Me, and P(p-PhOMe)(3) in acetone, the kinetics give a rate law indicating the reversible formation of an intermediate which goes irreversibly to the 1,2-disubstituted ruthenocene product. All three rate constants and their thermal activation parameters have been obtained for each of these reactions. For the P(p-PhOMe)(3) reaction, the volume of activation for each step has also been determined. The reaction of 2 and 3 with PBu(3)(n), PCy(3), PPhMe(2), and PMe(3) in CD3CN give a long-lived intermediate which also goes to the 1,2-disubstituted ruthenocene product. For the intermediates formed from 3, the kinetics of this last step have been studied to determine the rate constants and their thermal activation parameters. In the case of PBu(3)(n), the intermediate formed from 3 has been isolated and an X-ray structure determined, establishing that phosphine attack has occurred at the C5H4O ring.

  DOI：

  10.1021/ic960383v

文献信息

• Kinetics and Mechanism of Nucleophilic Substitutions on Coordinated Polyenes and Polyenyls. 3.¹ Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage and a Comparison with Reaction at C₅H₄O in [Ru(η⁵-C₅H₅)(η⁴-C₅H₄O)(L)]⁺ (L = CH₃CN, Pyridine, Thiourea)
  作者：Walter Simanko、Walter Tesch、Valentin N. Sapunov、Kurt Mereiter、Roland Schmid、Karl Kirchner、John Coddington、Scot Wherland

  DOI：10.1021/om980701t

  日期：1998.12.1

  Complexes of the types [Ru(η5-C5H5)(η4-C5H4O)]2(CF3SO3)2 (1) and [Ru(η5-C5H5)(η4-C5H4O)(L)]CF3SO3 (L = CH3CN (2), pyridine (3), thiourea (4)) react with tertiary phosphines to give (i) 1,1‘- (12) or (ii) 1,2-disubstituted ruthenocenes (13) depending primarily on the basicity of the entering phosphine and the nature of L. Path i proceeds via the intermediacy of [Ru(η3-C5H5)(η4-C5H4O)(PR3)]22+ (5) and

  该类型的复合物的[Ru（η 5 -C 5 H ^ 5）（η 4 -C 5 ħ 4 O）] 2（CF 3 SO 3）2（1）和[茹（η 5 -C 5 H ^ 5）（ η 4 -C 5 ħ 4 O）（L）] CF 3 SO 3（L = CH 3 CN（2），吡啶（3），硫脲（4）），与叔膦反应，得到（ⅰ）1,1' -（12）或（ii）1,2-二取代ruthenocenes（13主要在进入磷化氢的碱度和L.路径的性质通过我的中间性进行视）的[Ru（η 3 -C 5 ħ 5）（η 4 -C 5 ħ 4 O）（PR 3）] 2 2+（5）和[茹（η 3 -C 5 ħ 5）（η 4 -C 5 ħ 4 O）（PR 3）（L）] +（6 - 8）; 即C 5 H的触觉5配体选自η改变5至η 3而形成附加的Ru-P键。的η 3通过建立键合方式1 H和13 C 1 1个H} NMR光谱。详细研究了这些反应的
• Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy
  作者：Walter Simanko、Valentin N. Sapunov、Roland Schmid、Karl Kirchner、Scot Wherland

  DOI：10.1021/om9801195

  日期：1998.6.1

  The kinetics of the reactions of the complexes [Ru(eta(5)-C5H5)(eta(4)-C5H4O)(L)]CF3SO3 (L = CH3CN, pyridine, thiourea) with PMe3 have been, studied in acetone. The novel reaction, products [Ru(eta(3)-C5H5)(eta(4)-C5H4O)(PMe3)(L)]CF3SO3 formed are fluxional in solution due to an intramolecular enantiomeric equilibrium likely proceeding through a five-coordinate eta(1)-C5H5 intermediate.