[RuCl(η5-indenyl)(HPiPr2)(PPh3)] | 934199-83-4

• 英文名称: [RuCl(η5-indenyl)(HPiPr2)(PPh3)]
• 英文别名: [Ru(η5-indenyl)Cl(HP-i-Pr2)(PPh3)]
• CAS: 934199-83-4
• 化学式: C₃₃H₃₇ClP₂Ru
• 分子量: 632.127
• InChiKey: GVINXXMEERWFLV-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：

  [RuCl(η5-indenyl)(HPiPr2)(PPh3)] 在 (CH₃)3COK 作用下， 以 甲苯 为溶剂， 生成 [Ru(η5-indenyl)(diisopropylphosphido)(triphenylphosphine)] 、 [RuH(η5-indenyl)(PiPr(C(CH3)2))(PPh3)] 、 [RuCl(η5-indenyl)(HPiPr2)(κ2-(o-C6H4)PPh2)]
  参考文献：
  名称：

  A Highly Reactive Ruthenium Phosphido Complex Exhibiting Ru−P π-Bonding

  摘要：

  Multiple bonding in the terminal phosphido complex [Ru(PCy2)(eta(5)-indenyl)(PPh3)] (2a) is clearly demonstrated by solution, solid-state, and computational studies. Reactions of this dark blue, half-sandwich complex with CO, MeI, HNEt3Cl, HCl, NH4PF6, H-2, and Et3SiH demonstrate an unusual range of behavior resulting from combined coordinative unsaturation at Ru, high nucleophilicity/basicity of the phosphido P, and pi-character of the Ru-P interaction. The terminal, pi-bound phosphido structure is general for a range of PR2 species (R = Pr-i (2b), Ph (2c), Tol(p) (2d)). The very reactive diarylphosphido analogues 2c,d have been observed spectroscopically at low temperatures and can be trapped quantitatively as their CO adducts, [Ru(PAr2)(eta(5)-indenyl)(CO)(PPh3)] (3c,d), in which the Ru-P bond order is reduced to 1. Complex 2a and its analogue [Ru(PPr2i)(eta(5)-indenyl)(PPh3)] (2b) are consistently isolated with similar to 15% of their structural isomers, the ruthenium hydrido phosphaalkenes 9a, b, resulting from an apparent 1,2-H shift.

  DOI：

  10.1021/om0700056

文献信息

• Ruthenated Acetonitrile: Unusual Brønsted Acidity of a Polar “Aprotic” Solvent
  作者：Eric J. Derrah、Karina E. Giesbrecht、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/om800343x

  日期：2008.10.13

  benzonitrile and pyridine adducts, suggest that the metalation of acetonitrile by 1 proceeds via an intermolecular C−H addition across the Ru═P double bond, rather than the intramolecular C−H activation of N-bound acetonitrile. This is confirmed by the observation, by 31P1H} NMR, of multiple product isotopomers in the reaction of 1 with a 1:1 mixture of d3- and d0-acetonitrile. O-Donor solvents also deprotonated

  加入乙腈至复杂的[Ru（η 5 -茚基）（PR 2）（PPH 3）]（1）给出了不寻常的金属化产物的[Ru（η 5 -茚基）（CH 2 CN）（HPR 2）（PPH 3）]（2），其已在结构上进行了表征。该反应清楚地表明在1的末端磷酸配体上具有很高的布朗斯台德碱度。31 p 1个H} NMR研究表明，较低的酸性N-供体的溶剂简单地破坏在RU-Pπ键1，得到的加合物的[Ru（η 5 -茚基）（L）（HPR 2）（PPH 3）]（L =苄腈（6）或吡啶（7）），这是处于平衡1和自由L的类似乙腈加合物（4）的形成过程中，在240 K内由NMR中观察到2，但快速更换在较高温度下降低2倍。替代路线向金属化的络合物的NMR研究2中，从阳离子N-结合乙腈加合物开始的[Ru（η 5 -茚基）（NCCH 3）（HPCY 2）（PPH 3）] [PF 6 ]（3A），以及已证明的苄腈和吡啶加合物的不稳定性