bis{phenyl(2-picolyl)phosphine}propane | 1491145-62-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: bis{phenyl(2-picolyl)phosphine}propane
• 英文别名: Phenyl-[3-[phenyl(pyridin-2-ylmethyl)phosphanyl]propyl]-(pyridin-2-ylmethyl)phosphane；phenyl-[3-[phenyl(pyridin-2-ylmethyl)phosphanyl]propyl]-(pyridin-2-ylmethyl)phosphane
• CAS: 1491145-62-0；1491145-99-3
• 化学式: C₂₇H₂₈N₂P₂
• 分子量: 442.48
• InChiKey: NJMNHHJLPUKMIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis{phenyl(2-picolyl)phosphine}propane 在 盐酸 作用下， 以 乙醚 为溶剂， 以76%的产率得到bis{phenyl(2-picolyl)phosphine}propane dihydrochloride
  参考文献：
  名称：

  Configurational Isomerization of Dinuclear Iridium and Rhodium Complexes with a Series of NPPN Ligands, 2-PyCH₂(Ph)P(CH₂)_nP(Ph)CH₂-2-Py (Py = Pyridyl, n = 2–4)

  摘要：

  New heterodonor NPPN tetradentate ligands, 2-PyCH2(Ph)P-(CH2)(n) P(Ph)CH2-2-Py (meso- and rac-L-n; n = 2-4, Py = pyridyl), were prepared and reacted with [Cp*MCl2](2) (M = Ir, Rh; Cp* is pentamethylcyclopentadienyl) in the presence of NH4BF4 to afford a series of dinuclear complexes [(Cp*MCl)(2)(meso-L-n)](BF4)(2) (M = Ir, n = 2 (2a), 3 (3a), 4 (4a); M = Rh, n = 2 (2c), 3 (3c), 4 (4c)) and [(Cp*MCl)(2)(rac-L-n)](BF4)(2) (M = Ir, n = 2 (2b), 3 (3b), 4 (4b); M = Rh, n =, 2 (2d), 3 (3d), 4 (4d)), which were characterized by IR, H-1 and (31)p{H-1} NMR, and ESI mass spectroscopic techniques and X-ray crystallography. The configurations around the two metal centers were controlled by the configuration of the coordinated P atoms so as to avoid repulsive interaction between the phenyl group on P and the chloride ligand, resulting in the formation of stereospecific isomers; a mesa configuration of the metal centers is induced from meso-L-n (abbreviated as meso-P-2/meso-M-2), and in contrast, a rac configuration is induced from rac-L" (rac-P-2/rac-M-2). Furthermore, inversion of metal centers for the Ir-2 complexes occurred in DMSO at higher temperatures (60-100 degrees C), generating equilibrium mixtures of minor diastereomers (meso-P-2/rac-M-2 or rac-P-2/meso-M-2) in low ratios together with the major isomers (meso-P-2/meso-M-2 or rac-P-2/rac-M-2). The equilibrium constants, K = [minor isomer]/[major isomer], varied appreciably depending on the lengths of the methylene chains as well as configurations of the NPPN ligands; the overall propensity for the K values was observed to be L-2 < L-3

  DOI：

  10.1021/om400965j
• 作为产物：
  描述：

  2-氯甲基吡啶 、 1,3-双(苯基膦酰)丙烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以81%的产率得到bis{phenyl(2-picolyl)phosphine}propane
  参考文献：
  名称：

  Configurational Isomerization of Dinuclear Iridium and Rhodium Complexes with a Series of NPPN Ligands, 2-PyCH₂(Ph)P(CH₂)_nP(Ph)CH₂-2-Py (Py = Pyridyl, n = 2–4)

  摘要：

  New heterodonor NPPN tetradentate ligands, 2-PyCH2(Ph)P-(CH2)(n) P(Ph)CH2-2-Py (meso- and rac-L-n; n = 2-4, Py = pyridyl), were prepared and reacted with [Cp*MCl2](2) (M = Ir, Rh; Cp* is pentamethylcyclopentadienyl) in the presence of NH4BF4 to afford a series of dinuclear complexes [(Cp*MCl)(2)(meso-L-n)](BF4)(2) (M = Ir, n = 2 (2a), 3 (3a), 4 (4a); M = Rh, n = 2 (2c), 3 (3c), 4 (4c)) and [(Cp*MCl)(2)(rac-L-n)](BF4)(2) (M = Ir, n = 2 (2b), 3 (3b), 4 (4b); M = Rh, n =, 2 (2d), 3 (3d), 4 (4d)), which were characterized by IR, H-1 and (31)p{H-1} NMR, and ESI mass spectroscopic techniques and X-ray crystallography. The configurations around the two metal centers were controlled by the configuration of the coordinated P atoms so as to avoid repulsive interaction between the phenyl group on P and the chloride ligand, resulting in the formation of stereospecific isomers; a mesa configuration of the metal centers is induced from meso-L-n (abbreviated as meso-P-2/meso-M-2), and in contrast, a rac configuration is induced from rac-L" (rac-P-2/rac-M-2). Furthermore, inversion of metal centers for the Ir-2 complexes occurred in DMSO at higher temperatures (60-100 degrees C), generating equilibrium mixtures of minor diastereomers (meso-P-2/rac-M-2 or rac-P-2/meso-M-2) in low ratios together with the major isomers (meso-P-2/meso-M-2 or rac-P-2/rac-M-2). The equilibrium constants, K = [minor isomer]/[major isomer], varied appreciably depending on the lengths of the methylene chains as well as configurations of the NPPN ligands; the overall propensity for the K values was observed to be L-2 < L-3

  DOI：

  10.1021/om400965j

文献信息

• Configurational Isomerization of Dinuclear Iridium and Rhodium Complexes with a Series of NPPN Ligands, 2-PyCH₂(Ph)P(CH₂)_<i>n</i>P(Ph)CH₂-2-Py (Py = Pyridyl, <i>n</i> = 2–4)
  作者：Takayuki Nakajima、Yuki Fukushima、Minori Tsuji、Naoko Hamada、Bunsho Kure、Tomoaki Tanase

  DOI：10.1021/om400965j

  日期：2013.12.23

  New heterodonor NPPN tetradentate ligands, 2-PyCH2(Ph)P-(CH2)(n) P(Ph)CH2-2-Py (meso- and rac-L-n; n = 2-4, Py = pyridyl), were prepared and reacted with [Cp*MCl2](2) (M = Ir, Rh; Cp* is pentamethylcyclopentadienyl) in the presence of NH4BF4 to afford a series of dinuclear complexes [(Cp*MCl)(2)(meso-L-n)](BF4)(2) (M = Ir, n = 2 (2a), 3 (3a), 4 (4a); M = Rh, n = 2 (2c), 3 (3c), 4 (4c)) and [(Cp*MCl)(2)(rac-L-n)](BF4)(2) (M = Ir, n = 2 (2b), 3 (3b), 4 (4b); M = Rh, n =, 2 (2d), 3 (3d), 4 (4d)), which were characterized by IR, H-1 and (31)pH-1} NMR, and ESI mass spectroscopic techniques and X-ray crystallography. The configurations around the two metal centers were controlled by the configuration of the coordinated P atoms so as to avoid repulsive interaction between the phenyl group on P and the chloride ligand, resulting in the formation of stereospecific isomers; a mesa configuration of the metal centers is induced from meso-L-n (abbreviated as meso-P-2/meso-M-2), and in contrast, a rac configuration is induced from rac-L" (rac-P-2/rac-M-2). Furthermore, inversion of metal centers for the Ir-2 complexes occurred in DMSO at higher temperatures (60-100 degrees C), generating equilibrium mixtures of minor diastereomers (meso-P-2/rac-M-2 or rac-P-2/meso-M-2) in low ratios together with the major isomers (meso-P-2/meso-M-2 or rac-P-2/rac-M-2). The equilibrium constants, K = [minor isomer]/[major isomer], varied appreciably depending on the lengths of the methylene chains as well as configurations of the NPPN ligands; the overall propensity for the K values was observed to be L-2 < L-3