[ruthenium(II)(η6-p-cymene)Cl(κ2-P,O-Ph2PCH2P(=NP(O)(OPh)2)Ph2)][SbF6] | 540518-59-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [ruthenium(II)(η6-p-cymene)Cl(κ2-P,O-Ph2PCH2P(=NP(O)(OPh)2)Ph2)][SbF6]
• 英文别名: [RuCl(η6-p-cymene)(κ2-P,O-Ph2PCH2P(=NP(=O)(OPh)2)Ph2)][SbF6]；chlororuthenium(1+);diphenoxyphosphorylimino-(diphenylphosphanylmethyl)-diphenyl-λ5-phosphane;hexafluoroantimony(1-);1-methyl-4-propan-2-ylbenzene
• CAS: 540518-59-0
• 化学式: C₄₇H₄₆ClNO₃P₃Ru*F₆Sb
• 分子量: 1138.07
• InChiKey: PNODQOHZLMCCKX-UHFFFAOYSA-G

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [ruthenium(II)(η6-p-cymene)Cl(κ2-P,O-Ph2PCH2P(=NP(O)(OPh)2)Ph2)][SbF6] 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到[RuCl(η6-p-cymene)(κ2-P,C-Ph2PCHP(=NP(=O)(OPh)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
• 作为产物：
  描述：

  盐酸 、 [Ru(η6-p-cymene)(κ3-P,C,O-Ph2PCHP(=NP(=O)(OPh)2)Ph2)][SbF6]*0.25(dichloromethane) 以 二氯甲烷 为溶剂， 生成 [ruthenium(II)(η6-p-cymene)Cl(κ2-P,O-Ph2PCH2P(=NP(O)(OPh)2)Ph2)][SbF6]
  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

文献信息

• Ruthenium(II) and Ruthenium(IV) Complexes Containing κ¹-<i>P</i>-, κ²-<i>P,O</i>-, and κ³-<i>P,N</i><i>,</i><i>O</i>-Iminophosphorane-Phosphine Ligands Ph₂PCH₂P{NP(O)(OR)₂}Ph₂ (R = Et, Ph):  Synthesis, Reactivity, Theoretical Studies, and Catalytic Activity in Transfer Hydrogenation of Cyclohexanone
  作者：Victorio Cadierno、Pascale Crochet、Josefina Díez、Joaquín García-Álvarez、Sergio E. García-Garrido、José Gimeno、Santiago García-Granda、Miguel A. Rodríguez

  DOI：10.1021/ic020702k

  日期：2003.5.1

  selectively formed from 2b and 6a,b. Complexes [Ru(eta(6)-p-cymene)(kappa(3)-P,N,O-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))][SbF(6)](2 ) (R = Et (5a), Ph (5b)) and [Ru(eta(3):eta(3)-C(10)H(16))(kappa(3)-P,N,O-Ph(2)PCH(2)P[=NP(=O)(OR)(2)]Ph(2))][ SbF(6)](2) (R = Et (8a), Ph (8b)) have been prepared using 2 equiv of AgSbF(6). The reactivity of 3-5a,b has been explored allowing the synthesis of [Ru(eta(6)-p-cymene)X(

  [[Ru（eta（6）-p-cymene）（mu-Cl）Cl）（2）]和[[Ru（eta（3）：eta（3）-C（10）H（16））（mu -Cl）Cl）（2）]与Ph（2）PCH（2）P [= NP（= O）（OR）（2）] Ph（2）反应（R = Et（1a），Ph（1b） ），提供络合物[Ru（eta（6）-p-cymene）Cl（2）（kappa（1）-P-Ph（2）PCH（2）P [= NP（= O）（OR）（2）] Ph（2））]（R = Et（2a），Ph（2b））和[Ru（eta（3）：eta（3）-C（10）H（16））Cl（2）（kappa（1） ）-P-Ph（2）PCH（2）P [= NP（= O）（OR）（2）] Ph（2））]（R = Et（6a），Ph（6b））。用1当量的AgSbF（6）处理2a会产生[Ru（eta（6）-p-cymene）Cl（kappa（2）-P，O-Ph（2）PCH（2）P