(η5-C5Me5)Ru[κ3-P(i)Pr2(MeC=CH2)]H | 1268164-32-4

• 英文名称: (η5-C5Me5)Ru[κ3-P(i)Pr2(MeC=CH2)]H
• CAS: 1268164-32-4
• 化学式: C₁₉H₃₅PRu
• 分子量: 395.531
• InChiKey: XIYZZTPTFCUHJY-UHFFFAOYSA-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：

  (η5-C5Me5)Ru(P(i)Pr3)(BH3(2,4,6-trimethylphenyl)) 在 norbornene or CH₂CHC(CH₃)3 作用下， 以 not given 为溶剂， 生成 (η5-C5Me5)Ru[κ3-P(i)Pr2(MeC=CH2)]H
  参考文献：
  名称：

  Probing Mesitylborane and Mesitylborate Ligation Within the Coordination Sphere of Cp*Ru(PⁱPr₃)⁺: A Combined Synthetic, X-ray Crystallographic, and Computational Study

  摘要：

  The reaction of Cp*Ru((PPr3)-Pr-i)Cl (1) with MesBH(2) (Mes = 2,4,6-trimethylphenyl) afforded the mesitylborate complex Cp*Ru((PPr3)-Pr-i)(BH(2)MesCl) (2, 66%). Exposure of 2 to the chloride abstracting agent LiB(C6F5)(4)center dot 2.50Et(2) provided [Cp*Ru((PPr3)-Pr-i)(BH(2)Mes)]B+(C6F5)(4) (3, 54%), which features an unusual eta(2)-B-H monoborane ligand. The related borate complex Cp*Ru((PPr3)-Pr-i)(BH(3)Mes) (5, 65%) was prepared from 1 and LiH(3)BMes. Attempts to effect the insertion of unsaturated organic substrates into the B-H bonds of 3 were unsuccessful, and efforts to dehydrohalogenate 2 using (KOBu)-Bu-i instead afforded the mesitylborate complex Cp*((PPr3)-Pr-i)Ru(BH(2)MesOH) (6, 48%). Treatment of 1 with benzyl potassium generated an intermediate hydridoruthenium complex (7) resulting from dehydrogenation of a (PPr)-Pr-i fragment, which in turn was observed to react with MesBH(2) to afford the mesitylborate complex Cp*(P(Pr-i)(2)(CH3CCH2))Ru(BH(3)Mes) (8, 47%). Crystallographic characterization data are provided for 2, 3, 5, 6, and 8. A combined X-ray crystallographic and density functional theory (DFT) investigation of 3 and 5, using Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analysis, revealed that 3 and 5 are best described as donor acceptor complexes between a Cp*((PPr3)-Pr-i)Ru fragment and a bis(eta(2)-B-H) coordinating mesitylborane(borate) ligand. Significant sigma-donation from the B-H bonds into the Ru-II center exists as evidenced by the NBO populations, bond orders, and AIM delocalization indices. In the case of 3, the vacant p orbital on boron is stabilized by Ru -> B pi back-donation as well as by resonance with the mesityl group.

  DOI：

  10.1021/ic1022328