Ru(C5(CH3)4(CH2C6H5))(Ph2PCH2CH2PPh(o-C6H4)-PPh) | 1579211-24-7

• 英文名称: Ru(C5(CH3)4(CH2C6H5))(Ph2PCH2CH2PPh(o-C6H4)-PPh)
• CAS: 1579211-24-7
• 化学式: C₄₈H₄₇P₃Ru
• 分子量: 817.892
• InChiKey: MCIVALQPROWYQB-TZDZJGMTSA-N

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

• 作为产物：
  描述：

  [Ru(η⁵-C₅Me₅)(1,2-bis(diphenylphosphino)ethene)(PPh₂)] 以 甲苯 、 正戊烷 为溶剂， 以93%的产率得到Ru(C5(CH3)4(CH2C6H5))(Ph2PCH2CH2PPh(o-C6H4)-PPh)
  参考文献：
  名称：

  Reactivity of Ruthenium Phosphido Species Generated through the Deprotonation of a Tripodal Phosphine Ligand and Implications for Hydrophosphination

  摘要：

  The fragmentation of the 1,1,2-tris(diphenylphosphino)ethane ligand in [RuCp*((Ph2P)(2)CHCH2PPh2)][PF6] (1) was explored through treatment with base under aprotic conditions. The neutral phosphido complex RuCp*(PPh2CH=CHPPh2) (PPh2) (2) with a (Z)-1,2-bis(diphenylphosphino)ethene (dppen) ligand was generated through a base-facilitated dehydrophosphination reaction. Installation of a bis(p-tolyl)phosphido ligand was attempted by combining bis(p-tolyl)phosphine with RuCp*(dppen)Cl in the presence of KOtBu, but surprisingly, the unsymmetrical diphenylphosphido compound RuCp*(Ph2PCHCHP-(p-tol)(2))(PPh2) (5) was generated instead. The ligand rearrangement reaction was driven by the greater electron density on the bis(p-tolyl)phosphido moiety. Density functional theory calculations showed that fragmentation to the 1,2-disubstituted ligand was thermodynamically favored over the 1,1-disubstituted ligand and that intramolecular phosphido exchange was kinetically accessible at room temperature. The greater basicity of the bis(p-tolyl)phosphido ligand was experimentally verified by the measured pK(a)(THF) of 28 for the acid/base pair [RuCp*(Ph2P(o-C6H2OPPh2)(P(p-tolyl)(2)H)](+)/RuCp*(Ph2P(o-C6H4)PPh2)(P(p-tolyl)(2)) versus 25 for the acid/base pair [RuCp*(Ph2P(o-C6H4)PPh2)(PPh2H)]+/RuCp*(Ph2P(o-C6H4)PPh2)(PPh2) (7). For comparison, the approximate pK(a)(THF) values for free P(p-tolyl)(2)H/[K(crypt)]P(p-tolyl)(2) and free PPh2H/[K(crypt)]PPh2 are 43 and 38, respectively. This is the first quantitative measurement of the large effect that coordination to a metal center, in this case ruthenium(II), has on the acidity of secondary phosphines. This is useful information for designing and understanding hydrophosphination catalysts. Complexes 2 and 7 are catalysts for the addition of PPh2H to acrylonitrile, but they deactivate fairly rapidly. The pK(a)(THF) measurements are consistent with a catalytic cycle involving a Michael addition step. Complex 2 in solution underwent a slow, unprecedented rearrangement of P C, C C, and C H bonds to give crystalline Ru(C-5(CH3)(4)(CH2C6H5))(Ph2PCH2CH2PPh(o-C6H4)PPh) (9) in high yields, demonstrating the unpredictable reactivity of phosphido ligands.

  DOI：

  10.1021/ja5006724