[(η6-C6Me6)Cl(diphenylvinylphosphine)Ru(CO)]PF6 | 312963-08-9

• 英文名称: [(η6-C6Me6)Cl(diphenylvinylphosphine)Ru(CO)]PF6
• CAS: 312963-08-9
• 化学式: C₂₇H₃₁ClOPRu*F₆P
• 分子量: 684.003
• InChiKey: BHCNGZSSPZONPV-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

• 作为产物：
  描述：

  acetonitrile;chlororuthenium(1+);ethenyl(diphenyl)phosphane;1,2,3,4,5,6-hexamethylbenzene;hexafluorophosphate 、 一氧化碳 以 丙酮 为溶剂， 以86.9%的产率得到[(η6-C6Me6)Cl(diphenylvinylphosphine)Ru(CO)]PF6
  参考文献：
  名称：

  Novel Ruthenium(II) Carbene Complexes:  Products of the Reactions of 1-Alkynes with (η⁶-C₆Me₆)Cl₂Ru(PR₃)

  摘要：

  The complexes (eta6-C6Me6)Cl2RU(PR3) (1; PR3 = DPVP (diphenylvinylphosphine) (a), PMe3 (b), PPh3 (c)) react with NaPF6 in acetonitrile solutions to give the cationic complexes [(eta (6)-C6Me6)ClRu(PR3)(NCCH3)]PF6 (2a-c) by loss of NaCl, Complexes la and 2a react with HC=CSiMe3 and HC=CPh land NaPF6 for 1a) in MeOH to give the carbene complexes [(eta (6)-C6Me6)Cl(DPVP)Ru=C (OCH3)CH3]PF6 (3a) and [(eta (6)-C6Me6) Cl(DPVP)Ru=C(OCH3)CH2Ph]PF6 (4a), respectively. The known analogues 3b,c and 4b and the new complex 4c have been synthesized from 2b,c and HC drop CR. The solid-state structures of these complexes show a wide variation in the orientation of the carbene plane with respect to the plane of the eta (6)-arene ring (dihedral angles of 37,9-59,6 degrees) The solution dynamic behavior of 3a-c and 4a-c is discussed, Complex 2a also reacts with HC drop CCH2CH2OH in MeOH to give the oxacyclic carbene complex [(eta (6)-C6Me6)Cl(DPVP)Ru=C(CH2CH2CH2)O]PF6 (5). 1a (and NaPF6) and 2a react with HC=CC(OH)Ph-2 in MeOH to give the novel phosphorus ylide complex [(eta (6)-C6Me6)ClRuC(=C=CPh2)PPh2CH=CH2]PF6 (6) and with dimethylpropargylamine in CH2Cl2 or dichloroethane to give the amino cyclic carbene complex [(eta (6)- C6Me6)Cl(DPVP)Ru= CCH2- CMe2NH]PFG (7) and the metallacyclic complex [(r76-CsMes)C1RuCH=C(DPVP)CMe2NH21PFB (8). In the absence of MeOH, reaction of 2a with HC=CC(OH)Ph-2 gives the dimeric complex [(eta (6)-C6Me6)Ru(mu -Cl)(3)Ru(eta (6)-C6Me6)]PF6. Complex 2a plus HC=CPh in the absence of MeOH gives the carbonyl complex [(eta (6)-C6Me6)Cl(DPVP)Ru(CO)]PF6 (9), Reaction of 2c with HC=CPh in MeOH for extended time periods (>1 day) gives an analogous carbonyl complex of PPh3, [(eta (6)-C6Me6)Cl(PPh3)Ru(CO)]PF6. All complexes have been characterized by H-1, C-13{1H}, and P-31{H-1} NMR and IR spectroscopies and electrochemistry and in most cases by X-ray crystallography. Complex la is an efficient catalyst for the regioselective addition of H2O to HC=CPh, producing exclusively acetophenone in 70% isolated yield.

  DOI：

  10.1021/om0004949