Bis[2-bis(4-methoxyphenyl)phosphanylethyl]-phenylphosphane | 235421-99-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: Bis[2-bis(4-methoxyphenyl)phosphanylethyl]-phenylphosphane
• CAS: 235421-99-5
• 化学式: C₃₈H₄₁O₄P₃
• 分子量: 654.662
• InChiKey: SEQGHZGKEDNCBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  45
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dichlorotetrakis(dimethylsulfoxide)ruthenium(II) 、 Bis[2-bis(4-methoxyphenyl)phosphanylethyl]-phenylphosphane 以 甲苯 为溶剂， 以76%的产率得到[Ru2(μ-Cl)3(PPh(CH2CH2P(p-MeOC6H4)2)2)2]Cl * 2 H2O
  参考文献：
  名称：

  Some new chain-like terdentate phosphines, their ruthenium(II) coordination chemistry and the activity of the cations [Ru(MeCN)3(PhP{CH2CH2P(p-X-C6H4)2}2)]2+ (X=H, F, Me and OMe) as acetalization catalysts

  摘要：

  The new chain-like tritertiary phosphines PhP{CH2CH2P(p-X-C6H4)(2)}(2), (X = F, Me and OMe), phetpX, were prepared and characterized. These ligands react with cis-[RuCl2(DMSO)(4)] giving equilibrium mixtures of the eclipsed (ec) and staggered (st) isomers of the dinuclear complexes [Ru-2(mu-Cl)(3)(phetpX)(2)]Cl. The preparation and characterization of the tritertiary phosphines MesP{CH2CH2P(p-X-C6H4)(2)}(2) (Mes = mesityl, X = H and Fl, mesetpX, is also reported. They react with cis-[RuCl2(DMSO)(4)] giving equilibrium mixtures of corresponding uninuclear, [RuCl2(mesetpX)], and dinuclear species, st-[Ru-2(mu-Cl)(3)(mesetpX)(2)]Cl, whose molecularities were established by determining their diffusion coefficients. The dissociation of st -[Ru-2(mu-Cl)(3)(mesetph)(2)]Cl to [RuCl2(mesetph)] (K = 1.8 x 10(-2) mol(-1)) is endothermic (Delta H = 32 kJ mol(-1)) and favored by entropy (Delta S = 75 J mol(-1)). The complexes 'RuCl2(pp(2))' (pp(2) = phetph, and mesetph) react with CO giving fac-[RuCl2(CO)(pp(2))] and fac-[RuCl(CO)(2)(pp(2))]Cl as kinetic products. These complexes slowly rearrange to the thermodynamically stable products mer-[RuCl2(CO)(pp(2))]. The complexes st-[Ru-2(mu-Cl)(3)(phetpX)(2)]Cl react with four equivalents of AgCF3SO3 in MeCN giving the corresponding salts [Ru(MeCN)(3)(phetpX)](CF3SO3)(2). Their activities as catalysts for the acetalization of cyclo-hexanone with 1,2-dihydroxyethane and the trans-acetalization of cyclo-hexanone with 2,2-dimethyl-1,3-dioxolane are described. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00117-6

文献信息

• Ancillary Ligand Effects on Carbon Dioxide-Ethylene Coupling at Zerovalent Molybdenum
  作者：Brian S. Hanna、Alex D. MacIntosh、Steven Ahn、Brian T. Tyler、G. Tayhas R. Palmore、Paul G. Williard、Wesley H. Bernskoetter

  DOI：10.1021/om500324h

  日期：2014.7.14

  A series of zerovalent molybdenum complexes bearing triphosphine ligands, [Ar2PCH2CH2](2)PPh, have been synthesized and evaluated for reductive functionalization of CO2 with ethylene. The ability to form dimeric triphosphine molybdenum(U) acrylate hydride species from CO2-ethylene coupling was found to be highly sensitive to steric encumbrance on the phosphine aryl substituents. Trapping of triphosphine molybdenum(II) acrylate hydride species using triphenylphosphine afforded isolable monomeric CO2 functionalization products with all ancillary ligands studied. Kinetic analysis of the acrylate formation reaction revealed a first-order dependence on molybdenum, but no influence from CO2 pressure or the triphenylphosphine trap. Systematic attenuation of steric and electronic features of the triphosphine ligands showed a strong CO2 functionalization rate influence for ligand size with [(3,5-Bu-t-C6H3)(2)PCH2CH2](2)PPh coupling nearly four times slower than with [(3,5-Me-C6H3)(2)PCH2CH2](2)PPh. A considerably milder electronic effect was observed with complexes bearing [(4-F-C6H4)(2)PCH2CH2](2)PPh reducing CO2 at approximately half the rate as with [Ph2PCH2CH2](2)PPh.