dichloro{2-(phenylvinylphosphino)-5,6-dimethyl-7-phenyl-7-phosphabicyclo{2.2.1}hept-5-ene}palladium(II) | 118245-58-2

• 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: dichloro{2-(phenylvinylphosphino)-5,6-dimethyl-7-phenyl-7-phosphabicyclo{2.2.1}hept-5-ene}palladium(II)
• CAS: 118245-58-2；140631-95-4；178456-28-5；98651-94-6
• 化学式: C₂₂H₂₄Cl₂P₂Pd
• 分子量: 527.706
• InChiKey: LRLULWCUJOISQL-GCILOLCCSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.98
• 重原子数：
  27.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  二(三苯基膦)环戊二烯基氯化钌(II) 、 dichloro{2-(phenylvinylphosphino)-5,6-dimethyl-7-phenyl-7-phosphabicyclo{2.2.1}hept-5-ene}palladium(II) 在 NaCN 作用下， 以 1,2-二氯乙烷 为溶剂， 生成
  参考文献：
  名称：

  [（η5-C5H5）Ru（DMPP）3-n（dienophile）n] PF6配位区内的分子内[4 + 2] Diels-Alder环加成反应的范围和非对映选择性

  摘要：

  The complex [(eta-5-C5H5)Ru(DMPP)2(CH3CN)]PF6 (1; DMPP = 1-phenyl-3,4-dimethylphosphole) reacts with the dieneophiles Ph2PCH=CH2 (DPVP), PhP(CH=CH2)2 (DVPP), PhP(CH2CH=CH2)2 (DAPP), PhS(O)CH=CH2, PhSCH=CH2, and 2-vinylpyridine to produce one (10, 12), two (4, 11), or three (5, 9) diastereomers of (eta-5-cyclopentadienyl)(1-phenyl-3,4-dimethylphosphole)[syn-exo-2-(diphenyl-phosphino)-5, 6-dimethyl-7-phenyl-7-phosphabicyclo[2.2.1]hept-5-ene]ruthenium(II) hexafluorophosphate (4a,b), (eta-5-cyclopentadienyl)(1-phenyl-3,4-dimethylphosphole)[syn-exo-2-(phenylvinylphosphino)-5,6-dimethyl-7-phenyl-7-phosphabicyclo [2.2.1]hept-5-ene]ruthenium(II) hexafluorophosphate (5a,b), (eta-5-cyclopentadienyl) {syn-exo-meso-phenylbis[5,6-dimethyl-7-phenyl-7-phosphabicyclo[2.2.l]hept-5-en-2-yl] phosphine}ruthenium(II) hexafluorophosphate (5c), (eta-5-cyclopentadienyl)(1-phenyl-3,4-dimethyl-phosphole) [syn-exo-2-((allylphenylphosphino)methyl)-5,6-dimethyl-7-phenyl-7-phosphabicyclo[2.2.1]-hept-5-ene] ruthenium(II) hexafluorophosphate (9a,b), (eta-5-cyclopentadienyl){syn-exo-dl-phenylbis[(5,6-dimethyl-7-phenyl-7-phosphabicyclo [2.2.1]hept-5-ene-2-yl]phosphine}ruthenium(II) hexafluorophosphate (9c), (eta-5-cyclopentadienyl)(1-phenyl-3,4-dimethylphosphole)[syn-exo-2-(phenylsulfinyl)-5,6-dimethyl-7-phenyl-7-phosphabicyclo [2.2.1]hept-5-ene]ruthenium(II) hexafluorophosphate (10), (eta-5-cyclo-pentadienyl) (1-phenyl-3,4-dimethylphosphole)[syn-exo-2-(phenylthio)-5,6-dimethyl-7-phenyl-7-phospha-bicyclo [2.2.1]hept-5-ene]ruthenium(II) hexafluorophosphate (11), (eta-5-cyclopentadienyl)[syn-exo-2-(2-pyridyl)5, 6-dimethyl-7-phenyl-7-phosphabicyclo[2.2.1]hept-5-ene]ruthenium(II) hexafluorophosphate (12), respectively, by intramolecular [4 + 2] Diels-Alder cycloadditions in high yields. Similar Diels-Alder cycloadditions occur with [(eta-5-C5H5)Ru(DPVP)2(CH3CN)]PF6 (2) and [(eta-5-C5H5)Ru(DVPP)2(CH3CN)]PF6 (3) and DMPP to form 6a,b and 7a,b, respectively. Reactions of 1 with the potential dienophilic ligands L = Me2NC(O)CH=CH2, PhS(O)2CH=CH2, P(OCH2CH=CH2)3, P(C=CPh)3, H2NCH2CH=CH2, N=C-CH=CH2, N(CH2C(CH3)=CH2)3, and C2H5OCH=CH2 produced the [(eta-5-C5H5)Ru(DMPP)2L)]PF6 complexes 14-21, which could not be induced to undergo subsequent [4 + 2] Diels-Alder cycloadditions. New complexes were characterized by elemental analyses, physical properties, cyclic voltammetry, infrared spectroscopy, and H-1, C-13{H-1}, P-31{H-1}, and in some cases by H-1{p-31} nuclear magnetic resonance spectroscopy. Complex 11 is stereochemically nonrigid with sulfur inversion occurring rapidly at room temperature; DELTA-G double dagger = 59.8 kJ mol-1. The structures of 4b, 5c, and 11 were confirmed by X-ray crystallography. They crystallize in the P2(1)/c, P2(1)/m, and C2/c space groups, respectively, in unit cells of the following dimensions: 4b, a = 20.965 (9) angstrom, b = 11.125 (4) angstrom, c = 21.678 (9) angstrom, beta = 118.26 (2)-degrees, rho(calcd) = 1.438 g cm-3, Z = 4; 5c, a = 11.137 (3) angstrom, b = 19.124 (5) angstrom, c = 8.686 (3) angstrom, beta = 102.93 (2)-degrees, rho(calcd) = 1.564 g cm-3, Z = 2; 11, a = 11.392 (2) angstrom, b = 19.018 (5) angstrom, c = 35.610 (8) angstrom, beta = 96.40 (2)-degrees, rho(calcd) = 1.429 g cm-3, Z = 8. Refinements converged to R(F) = 0.051, 0.042, and 0.048 for 4842, 1975, and 3178 independent observed (I greater-than-or-equal-to 3-sigma(I)) reflections, respectively.

  DOI：

  10.1021/om00041a018

文献信息

• Redistribution reactions of platinum(II) and palladium(II) phosphine complexes
  作者：Jeffrey A. Rahn、Mark S. Holt、John H. Nelson

  DOI：10.1016/s0277-5387(00)86441-4

  日期：1989.1

  Abstract Anion redistribution equilibria of the type (R 3 P) 2 MX 2 + (R 3 P) 2 MY 2 ⇆ 2(R 3 P) 2 MXY (X, Y = Cl, Br, I, CN, N 3 ; R 3 P = Me 2 PhP, MePh 2 P, (Bzl) 3 P, (CH 2 CH) 2 PhP, (CH 2 CH)Ph 2 P and 1-phenyl-3,4-dimethylphosphole; M = Pd, Pt) have been studied by 31 P 1 H} and in some cases 195 Pt 1 H} NMR spectroscopy. It was found that except for the two cases when R 3 P = MePh 2 P, M

  摘要（R 3 P）2 MX 2 +（R 3 P）2 MY 2⇆2（R 3 P）2 MXY（X，Y = Cl，Br，I，CN，N 3; R 3 P = Me 2 PhP，MePh 2 P，（Bzl）3 P，（CH 2 = CH）2 PhP，（CH 2 = CH）Ph 2 P和1-苯基-3,4-二甲基磷脂; M = Pd， Pt）已通过31 P 1 H}和某些情况下的195 Pt 1 H} NMR光谱进行了研究。发现除了两种情况，当R 3 P = MePh 2 P，M = Pd，X = Cl，Y = Br和R 3 P = Me 2 PhP，M = Pd，X = Cl，Y = Br时，重新分配通常是瞬时的。（R 3 P）2 PdCl 2 +（R 3 P）2 Pd（CN）2反应较慢，但已完成。相反，当一个阴离子为CN-时，即使一个月后，铂络合物也未观察到阴离子再分布。混合阴离子物质相对于对称物
• A Simple and Efficient Approach to a Rigid Diphosphine Ligand Containing Two Phosphorus and Three Carbon Stereogenic Centers by Means of a Palladium Complex Promoted Asymmetric Diels−Alder Reaction
  作者：S. Selvaratnam、K. F. Mok、Pak-Hing Leung、Andrew J. P. White、David J. Williams

  DOI：10.1021/ic951545a

  日期：1996.1.1