[RuCl(Ph)(CO){κ³-P,N,P'-CH₂(NCH₂PCy₂)₂C₁₀H₆}] | 1597445-32-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: [RuCl(Ph)(CO){κ³-P,N,P'-CH₂(NCH₂PCy₂)₂C₁₀H₆}]
• 英文别名: benzene;carbon monoxide;dicyclohexyl-[[3-(dicyclohexylphosphanylmethyl)-2H-perimidin-1-yl]methyl]phosphane;ruthenium(2+);chloride
• CAS: 1597445-32-3
• 化学式: C₄₄H₆₁ClN₂OP₂Ru
• 分子量: 832.452
• InChiKey: MNLPKWPJXPYFGF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.08
• 重原子数：
  51
• 可旋转键数：
  4
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  7.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [RuCl(Ph)(CO){κ³-P,N,P'-CH₂(NCH₂PCy₂)₂C₁₀H₆}] 以 甲苯 为溶剂， 反应 96.0h， 以64%的产率得到[RuHCl(CO){κ³-P,C,P'=C(NCH₂PCy₂)₂C₁₀H₆}]
  参考文献：
  名称：

  Dihydroperimidine-Derived PNP Pincer Complexes as Intermediates en Route to N-Heterocyclic Carbene Pincer Complexes

  摘要：

  The reaction of N,N'-bis(dicyclohexylphosphinomethyl)-dihydroperimidine (H2C(NCH2PCy2)(2)C10H6-1,8, 1a) with [RuCl2(PPh3)(3)] in THF affords the perimidinylidene-based N-heterocyclic carbene (per-NHC) pincer complex [RuCl2(OC4H8){=C(NCH2PCy2)(2)C10H6}] (2) via chelate-assisted double C H activation. In contrast, the reactions of the tetraphenyl analogue H2C(NCH2PPh2)(2)C10H6 (1b) with [RuCl2(PPh3)(3)] and of la with [RuCl(R)(CO)(PPh3)(2)] (R = Ph, CH=CHPh) do not result in C-H activation but rather give the asymmetric, PNP-coordinated complexes [RuCl2(PPh3){kappa P-3,N,P'-CH2(NCH2PPh2)(2)C10H6}] (3) and [RuCl(R)(CO)-{kappa(3) P,N,P'-CH2(NCH2PCY2)(2)C10H6}] (R = Ph (4), CH=CHPh (5)), respectively, in which the ruthenium migrates rapidly between nitrogen donors. This provides insight into the mechanistic pathway by which the proligands 1 undergo per-NHC formation, as demonstrated by the thermal conversion of 4 to [RuHCl(CO){=C(NCH2PCy2)(2)C10H6}] (6) and benzene.

  DOI：

  10.1021/om5000985
• 作为产物：
  描述：

  Ru(Ph)Cl(CO)(triphenylphosphine)2 、 N,N′-bis(dicyclohexylphoshinomethyl)-2,3-dihydroperimidine 以 四氢呋喃 为溶剂， 反应 2.0h， 以79%的产率得到[RuCl(Ph)(CO){κ³-P,N,P'-CH₂(NCH₂PCy₂)₂C₁₀H₆}]
  参考文献：
  名称：

  Dihydroperimidine-Derived PNP Pincer Complexes as Intermediates en Route to N-Heterocyclic Carbene Pincer Complexes

  摘要：

  The reaction of N,N'-bis(dicyclohexylphosphinomethyl)-dihydroperimidine (H2C(NCH2PCy2)(2)C10H6-1,8, 1a) with [RuCl2(PPh3)(3)] in THF affords the perimidinylidene-based N-heterocyclic carbene (per-NHC) pincer complex [RuCl2(OC4H8){=C(NCH2PCy2)(2)C10H6}] (2) via chelate-assisted double C H activation. In contrast, the reactions of the tetraphenyl analogue H2C(NCH2PPh2)(2)C10H6 (1b) with [RuCl2(PPh3)(3)] and of la with [RuCl(R)(CO)(PPh3)(2)] (R = Ph, CH=CHPh) do not result in C-H activation but rather give the asymmetric, PNP-coordinated complexes [RuCl2(PPh3){kappa P-3,N,P'-CH2(NCH2PPh2)(2)C10H6}] (3) and [RuCl(R)(CO)-{kappa(3) P,N,P'-CH2(NCH2PCY2)(2)C10H6}] (R = Ph (4), CH=CHPh (5)), respectively, in which the ruthenium migrates rapidly between nitrogen donors. This provides insight into the mechanistic pathway by which the proligands 1 undergo per-NHC formation, as demonstrated by the thermal conversion of 4 to [RuHCl(CO){=C(NCH2PCy2)(2)C10H6}] (6) and benzene.

  DOI：

  10.1021/om5000985

文献信息

• Ruthenium and osmium complexes of dihydroperimidine-based N-heterocyclic carbene pincer ligands
  作者：Caitlin M. A. McQueen、Anthony F. Hill、Chenxi Ma、Jas S. Ward

  DOI：10.1039/c5dt03728j

  日期：——

  (per-NHC) pincer complex [RuCl2(OC4H8)κ3-P,C,P′-C(NCH2PCy2)2C10H6}] (2), while the latter reaction provides the asymmetric PNP-coordinated complex [RuCl2(PPh3)κ3-P,N,P′-CH2(NCH2PPh2)2C10H6}] (3), in which no C–H activation has occurred. Subsequent reactions of the per-NHC complex 2 with carbon monoxide and mesityl isocyanide readily displaced the labile THF ligand to afford the complexes [RuCl2(CA)κ3-P

  的反应Ñ，Ñ双（膦）dihydroperimidine亲配体ħ 2 C（NCH 2 PR 2）2 Ç 10 ħ 6（R =赛扬1a中，R =苯基1B）与将[RuCl 2（PPH 3）3 ]给出明显不同的产品。螯合物辅助双C-H活化前得到（每NHC）基于perimidinylidene-N-杂环卡宾配合物钳形将[RuCl 2（OC 4 H ^ 8）κ 3 - P，Ç，P'C（NCH 2 PCY 2）2 Ç 10 ħ 6 }]（2），而后者反应提供非对称PNP配位的络合物将[RuCl 2（PPH 3）κ 3 - P，Ñ，P '-CH 2（NCH 2 PPh 2）2 C 10 H 6 }]（3），其中没有发生C–H活化。NHC复合物的后续反应2与一氧化碳和三甲苯基胩容易偏移的不稳定配体的THF，得到的复合物将[RuCl 2（CA）κ 3 - P，Ç，P ' - C（NCH 2 PCY 2）2