OsHClF(CCH3)(P(i)Pr3)2 | 479692-74-5

• 英文名称: OsHClF(CCH3)(P(i)Pr3)2
• CAS: 479692-74-5
• 化学式: C₂₀H₄₆ClFOsP₂
• 分子量: 593.184
• InChiKey: JWXMXGKRNHSITI-UHFFFAOYSA-L

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：

  OsH₃Cl(PⁱPr₃)₂ 、 偏氟乙烯 以 氘代甲苯 为溶剂， 生成 OsHClF(CCH3)(P(i)Pr3)2
  参考文献：
  名称：

  Vinyl C−F Cleavage by Os(H)₃Cl(PⁱPr₃)₂

  摘要：

  Os(H)(3)ClL2 (L = (PPr3)-Pr-i) reacts at 20 degreesC with vinyl fluoride in the time of mixing to produce OsHFCl(dropCCH(3))L-2 and H-2. In a competitive reaction, the liberated H-2 converts vinyl fluoride to C2H4 and HF in a reaction catalyzed by Os(H)(3)ClL2. A variable-temperature NMR study reveals these reactions proceed through the common intermediate OsHCl(H-2)(H2C=CHF)L-2, via OsClF(=CHMe)L-2 and OsHCl(H-2)(C2H4)L-2, all of which are detected. DFT(B3PW91) calculations of the potential energy and free energy at 298 K of possible intermediates show the importance of entropy to account for their thermodynamic accessibility. Calculations of unimolecular C-F cleavage of coordinated C2H3F confirms the high activation energy of this process. Catalysis by HF is thus suggested to account for the fast observed reactions, and scavenging of HF with NEt3 changes the product to exclusively Os(H)(2)Cl(CCH3)L-2. The analogous reaction of Os(H)(3)ClL2 with H2C=CF2 produces exclusively OsHFCl(=CCH3)L-2 and HF, and the latter is again suggested to catalyze C-F scission via the observed intermediates Os(H)(2)Cl(CF2CH3)L-2 and OsHCl(=CFMe)L-2.

  DOI：

  10.1021/ic020365f