Ru(PCHtBu)Cl(CO)(CNC6H3Me2-2,6)(PPh3)2 | 176635-90-8

• 英文名称: Ru(PCHtBu)Cl(CO)(CNC6H3Me2-2,6)(PPh3)2
• CAS: 176635-90-8
• 化学式: C₅₁H₄₉ClNOP₃Ru
• 分子量: 921.4
• InChiKey: GXEFVTUDTGFYAI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Ru(PCHtBu)Cl(CO)(CNC6H3Me2-2,6)(PPh3)2 在 四氟硼酸-二乙醚络合物 、 potassium hydrogen difluoride 作用下， 生成
  参考文献：
  名称：

  Hydrochlorination of Ruthenaphosphaalkenyls: Unexpectedly Facile Access to Alkylchlorohydrophosphane Complexes

  摘要：

  The novel ruthenaphosphaalkenyls [Ru{P=C(H)SiMe2R}Cl-(Co)(PPh3)(2)] (R = p-C6H4CF3, Bu-n) have been prepared for the first time, and studied alongside precedent analogues (R = Me, Ph, p-tol) for their reactions with HCl. In contrast to chemistry defined for the tert-butyl congener [Ru{P,=C(H)Bu-t}CI(CO)(PPh3)(2)], which initially adds a single equivalent of HCI across the Ru-P linkage, all five silyl derivatives undergo spontaneous addition of a second equivalent to afford [Ru{eta(1)-PHCI-CH2SiMe2R}Cl(Co)(PPh3)(2)], extremely rare examples of coordinated "PHXR." type ligands. Where R = SiMe3, a distorted octahedral geometry with a conformationally restricted 'PHXR" ligand is observed crystallographically; this structure is appreciably retained in solution, as determined from multinuelear NMR spectroscopic features, which include a Karplus-like P-pph3-Ru-P-H spin-spin coupling dependence. Computational data suggest a silyl-induced increase in negative charge density at the phosphaalkenic carbon, rather than an intrinsic thermodynamic driver, as the likely origin of the disparate reactivity.

  DOI：

  10.1021/acs.organomet.6b00829
• 作为产物：
  描述：

  、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 以69%的产率得到Ru(PCHtBu)Cl(CO)(CNC6H3Me2-2,6)(PPh3)2
  参考文献：
  名称：

  磷炔加氢金属化：配合物[Ru（PCHCMe 3）Cl（CA）（PPh 3）2 ]的合成与反应性（A = O，S）

  摘要：

  [RuHCl（CO）（PPh 3）3 ]（1a）与P⋮CCMe 3的反应导致磷烯基络合物[Ru（P CHCMe 3）Cl（CO）（PPh 3）2 ]（2a）的形成。由于配位不饱和，2a与CO可逆反应以提供[Ru（P CHCMe 3）Cl（CO）2（PPh 3）2 ]（3），并与异腈（CNR）反应以提供[Ru（P CHCMe 3）Cl（CNR） ）（CO）（PPh 3）2 ] [R = CMe 3（4 a），C 6 H 3 Me 2 -2,6（4b）]。在过量的CNCMe 3中，获得了盐[Ru（P CHCMe 3）（CNR）2（CO）（PPh 3）2 ] Cl 5（Cl）。阴离子双齿配体K [H 2 B（bta）2 ]（bta =苯并三唑基）通过氯化物置换与2a反应生成[Ru（P CHCMe 3）{H 2 B（bta）2 }（CO）（PPh 3）2 ]（6），而面部三齿大环1,4,7-三硫代环壬烷（[9]

  DOI：

  10.1021/om980204c

文献信息

• Complete metal-mediated reduction of the triple bond of a phosphaalkyne: X-ray structure of [Ru(PHFCH₂Bu^t)Cl(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂]BF₄·CH₂Cl₂
  作者：Robin B. Bedford、David E. Hibbs、Anthony F. Hill、Michael B. Hursthouse、K. M. Abdul Malik、Cameron Jones

  DOI：10.1039/cc9960001895

  日期：——

  The reaction of [Ru(P=CHBu(t))Cl(CO)(CNC(6)H(3)Me(2)-2,6)(PPh(3))(2)] with HBF4 provides, rapidly and reversibly, the phosphaalkene complex [Ru(HP=CHBu(t))Cl(CO)(CNC(6)H(3)Me(2)-2,6)(PPh(3))(2)](+) which is converted by K[HF2] or [NBu(n)4]F to the structurally characterised fluorophosphine complex [Ru(PHFCH(2)Bu(t))Cl(CO)(CNC(6)H(3)Me(2)-2,6)(PPh(3))(2)](+).