[(η6-p-cymene)RuCl(η2-2,6-C5H3N(CH2OP(OC10H6)(μ-S)(C10H6O))2-κP,κP)]Cl | 934736-97-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [(η6-p-cymene)RuCl(η2-2,6-C5H3N(CH2OP(OC10H6)(μ-S)(C10H6O))2-κP,κP)]Cl
• 英文别名: 2,6-Bis(13,15-dioxa-2-thia-14-phosphapentacyclo[14.8.0.03,12.04,9.019,24]tetracosa-1(16),3(12),4,6,8,10,17,19,21,23-decaen-14-yloxymethyl)pyridine;dichlororuthenium;1-methyl-4-propan-2-ylbenzene
• CAS: 934736-97-7
• 化学式: C₅₇H₄₅ClNO₆P₂RuS₂*Cl
• 分子量: 1138.04
• InChiKey: LSPHJEUGKIQAIX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  18.92
• 重原子数：
  71
• 可旋转键数：
  7
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  119
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  2,6-C5H3N(CH2OP(OC10H6)(μ-S)(C10H6O))2 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 以 乙醇 为溶剂， 以88%的产率得到[(η6-p-cymene)RuCl(η2-2,6-C5H3N(CH2OP(OC10H6)(μ-S)(C10H6O))2-κP,κP)]Cl
  参考文献：
  名称：

  Large bite bisphosphite, 2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2: Synthesis, derivatization, transition metal chemistry and application towards hydrogenation of olefins

  摘要：

  Large bite bisphosphite ligand, 2,6-C5H3N(CH2OP(-OC10H6)(mu-S)(C10H6O-)}(2) (2), is obtained by reacting chlorophosphite, {-OC10H6(mu-S)C10H6O-}PCl (1) with 2,6-pyridinedimethanol in presence of triethylamine. Treatment of 2 with aqueous solution of H2O2 or elemental sulfur resulted in the formation of bis(oxide) or bis(sulfide) derivatives, 2,6-C5H3N{CH2OP(E)(-OC10H6)-(mu-S)(C10H6O-)}(2) (3, E=O; 4, E=S) in quantitative yield. The 10-membered cationic chelate complex, [RuCl(eta(6)-C10H14)eta(2)-2,6-C5H3N{CH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)-kappa P,kappa P]Cl (5) is produced in the reaction between [Ru(p-cymene)(mu-Cl)(Cl)](2) and bisphosphite 2, whereas the neutral chelate complex, eiv-[Rh(CO)Cl{2,6-C5H3N{CH2OP(-OC10H6(mu-S)C10H6O-)}(2)}-kappa P,kappa P] (6) is isolated in the reaction of 2 with 0.5 equiv. of [Rh(CO)(2)Cl](2). Compound 2 on treatment with M(COD)Cl-2 (M = Pd, Pt) produce the chelate complexes, [MCl2{eta(2)-2,6-C5H3N{CH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)}-kappa P,kappa P] (7, M = Pd; 10, M = Pt). Similarly the reaction of bisphosphite 2 with Pd(COD)MeCl affords cis-[PdMe(C1)eta(2)-2,6-C5H3N{CH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)-kappa P,kappa P] (8). Treatment of 2 with [Pd(eta(3)-C3H5)Cl](2) in the presence of AgClO4 furnish the cationic complex, [Pd(eta(3)-C3H5)eta(2)-2,6-C5H3N{CH2OP(-OC10H6)-(mu-S)(C10H6O-)}(2)-kappa P,kappa P]ClO4 (9). The binuclear complex, [Au2Cl2{2,6-C5H3N{CH2OP(-OC10H6)(mu-S)(C10H6O-)}2}-kappa P,kappa P] (11) is obtained in the reaction of compound 2 with two equiv. of AuCl(SMe2), where the ligand exhibits bridged bidentate mode of coordination . All the complexes are characterized by the H-1 NMR, P-31 NMR, elemental analysis and mass spectroscopy data. The cationic ruthe nium complex 5 is proved to be an active catalyst for the hydrogenation of styrene and alpha-methyl styrene. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.12.037

文献信息

• Large bite bisphosphite, 2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2: Synthesis, derivatization, transition metal chemistry and application towards hydrogenation of olefins
  作者：Benudhar Punji、Maravanji S. Balakrishna

  DOI：10.1016/j.jorganchem.2006.12.037

  日期：2007.3

  Large bite bisphosphite ligand, 2,6-C5H3N(CH2OP(-OC10H6)(mu-S)(C10H6O-)}(2) (2), is obtained by reacting chlorophosphite, -OC10H6(mu-S)C10H6O-}PCl (1) with 2,6-pyridinedimethanol in presence of triethylamine. Treatment of 2 with aqueous solution of H2O2 or elemental sulfur resulted in the formation of bis(oxide) or bis(sulfide) derivatives, 2,6-C5H3NCH2OP(E)(-OC10H6)-(mu-S)(C10H6O-)}(2) (3, E=O; 4, E=S) in quantitative yield. The 10-membered cationic chelate complex, [RuCl(eta(6)-C10H14)eta(2)-2,6-C5H3NCH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)-kappa P,kappa P]Cl (5) is produced in the reaction between [Ru(p-cymene)(mu-Cl)(Cl)](2) and bisphosphite 2, whereas the neutral chelate complex, eiv-[Rh(CO)Cl2,6-C5H3NCH2OP(-OC10H6(mu-S)C10H6O-)}(2)}-kappa P,kappa P] (6) is isolated in the reaction of 2 with 0.5 equiv. of [Rh(CO)(2)Cl](2). Compound 2 on treatment with M(COD)Cl-2 (M = Pd, Pt) produce the chelate complexes, [MCl2eta(2)-2,6-C5H3NCH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)}-kappa P,kappa P] (7, M = Pd; 10, M = Pt). Similarly the reaction of bisphosphite 2 with Pd(COD)MeCl affords cis-[PdMe(C1)eta(2)-2,6-C5H3NCH2OP(-OC10H6)(mu-S)(C10H6O-)}(2)-kappa P,kappa P] (8). Treatment of 2 with [Pd(eta(3)-C3H5)Cl](2) in the presence of AgClO4 furnish the cationic complex, [Pd(eta(3)-C3H5)eta(2)-2,6-C5H3NCH2OP(-OC10H6)-(mu-S)(C10H6O-)}(2)-kappa P,kappa P]ClO4 (9). The binuclear complex, [Au2Cl22,6-C5H3NCH2OP(-OC10H6)(mu-S)(C10H6O-)}2}-kappa P,kappa P] (11) is obtained in the reaction of compound 2 with two equiv. of AuCl(SMe2), where the ligand exhibits bridged bidentate mode of coordination . All the complexes are characterized by the H-1 NMR, P-31 NMR, elemental analysis and mass spectroscopy data. The cationic ruthe nium complex 5 is proved to be an active catalyst for the hydrogenation of styrene and alpha-methyl styrene. (c) 2006 Elsevier B.V. All rights reserved.