[RuCl(η6-p-cymene)(κ2-P,O-Ph2PCH2P(=NP(=O)(OEt)2)Ph2)][SbF6] | 540518-31-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [RuCl(η6-p-cymene)(κ2-P,O-Ph2PCH2P(=NP(=O)(OEt)2)Ph2)][SbF6]
• 英文别名: chlororuthenium(1+);diethoxyphosphorylimino-(diphenylphosphanylmethyl)-diphenyl-λ5-phosphane;hexafluoroantimony(1-);1-methyl-4-propan-2-ylbenzene
• CAS: 540518-31-8；540518-34-1
• 化学式: C₃₉H₄₆ClNO₃P₃Ru*F₆Sb
• 分子量: 1041.98
• InChiKey: LDYBROPRZMBFBD-UHFFFAOYSA-G

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

• 作为反应物：
  描述：

  [RuCl(η6-p-cymene)(κ2-P,O-Ph2PCH2P(=NP(=O)(OEt)2)Ph2)][SbF6] 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到[RuCl(η6-p-cymene)(κ2-P,C-Ph2PCHP(=NP(=O)(OEt)2)Ph2)]
  参考文献：
  名称：

  Base-Assisted Cyclometalation and Phosphorus−Carbon Bond Cleavage in (Arene)ruthenium(II) Complexes Containing Functionalized Iminophosphorane-Phosphine Ligands Ph₂PCH₂P{NP(X)(OR)₂}Ph₂ (X = O, S; R = Et, Ph)

  摘要：

  Complexes [RuCl(eta(6)-p-cymene)(kappa(2)-P,X-Ph2PCH2P{=NP(=X)(OR)(2)}Ph-2)][SbF6] (X = O, R = Et (1a), Ph (1b); X = S, R = Et (2a), Ph (2b)) react with a stoichiometric amount of NaH, in THF at rt, to generate the neutral cyclometalated compounds [RuCl(kappa(2)-P,C-Ph2PCHP-{=NP(=X)(OR)(2)}Ph-2)( eta(6)-p-cymene)] (X = O, R = Et (3a), Ph (3b); X = S, R = Et (4a), Ph (4b)), via selective deprotonation of the methylenic backbone of the coordinated iminophosphorane-phosphine ligands. Treatment of 3-4a,b with AgSbF6, in CH2Cl2 at rt, affords the corresponding cationic species [Ru(kappa(3)-P,C,X-Ph2PCHP{=NP(=X)(OR)(2)}Ph-2)(eta(6)-p-cymene)]-[SbF6] (X = O, R = Et (7a), Ph (7b); X = S, R = Et (8a), Ph (8b)) through the intramolecular O- or S-coordination of the free -Ph2P=NP(=X)(OR)(2) fragment. Complexes 7-8a,b can also be prepared by reaction of the dicationic derivatives [Ru(eta(6)-p-cymene)(kappa(3)-P,N,X-Ph2PCH2P-{=NP(=X)(OR)(2)}Ph-2)] [SbF6](2) (5-6a,b) with 1 equiv of NaH. Formation of complexes 3-4a,b and 7-8a,b proceeds, in all cases, in a diastereoselective manner. Phosphorus-carbon bond splitting has been observed upon treatment of complexes 1-2a,b, 3-4a,b, or 7-8a,b with an excess of NaH, in wet THF at rt, affording the novel phosphinito derivatives [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(=O)Ph-2}(eta(6) -p-cymene)] (X = O, R = Et (10a); X = S, R = Et (11a), Ph (11b)). Protonation and methylation of 10-11 a,b generates the cationic species [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(OH)Ph-2}(eta(6)-p-eymene)] [BF4] (X = O, R = Et (12a); X = S, R = Et (13a), Ph (13b)) and [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(OMe)Ph-2}(eta(6)-p-cymene)] [CF3SO3] (X = O, R = Et (14a); X = S, R = Et (15a), Ph (15b)), respectively, via selective electrophilic addition at the Ph2P=O group. The structure of compounds [RuCl(kappa(2)-P,C-Ph2PCHP{=NP(=O)(OPh)(2)}Ph-2)(eta(6)-p-cymene)] (3b) and [Ru(kappa(2)-C,S-CH2P{=NP(=S)(OEt)(2)}Ph-2){kappa(1)-P-P(=O)Ph-2}(eta(6)-C6H6)] (11a') has been determined by X-ray crystallography.

  DOI：

  10.1021/om040033d