PtCl2{(-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane}

• 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: PtCl2{(-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane}
• 英文别名: [Pt((2S,4S)-2,4-bis(diphenylphosphino)pentane)Cl2]；PtCl2((2S,4S)-2,4-bis(diphenylphosphino)pentane)；Dichloroplatinum;[(2S,4S)-4-diphenylphosphanylpentan-2-yl]-diphenylphosphane
• 化学式: C₂₉H₃₀Cl₂P₂Pt
• 分子量: 706.491
• InChiKey: CYJMLDPZGHDQOG-FQFBWUQZSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  PtCl2{(-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane} 、 2-二氮杂-1-苯乙酮 以 二氯甲烷 为溶剂， 以77%的产率得到
  参考文献：
  名称：

  非对映选择性卡宾插入铂-卤素键中。[PtCl（R-CHClCO2Et）（R，R-diop）的晶体结构

  摘要：

  Ethyl diazoacetate reacts with [PtX2L2] [X = Cl, Br, 1; L2 = 1,5-cyclooctadiene (cod), 2 PPh3, Ph2P-(CH2)nPPh2, n = 1 (dppm), 2 (dppe), 3 (dppp), 4 (dppb)] to give the corresponding [PtX(CHXCO2Et)L2] as a racemic mixture in high yields. The cod ligands in [PtX(CHXCO2Et)(cod)] are readily displaced by PPh3 or diphosphines. When optically active complexes [PtX2L*] (X = Cl, I; L* = R,R-diop, S,S-chiraphos, S,S-skewphos) were treated with ethyl diazoacetate, the products (PtX(CHXCO2Et)L*] were mixtures of diastereoisomers in different proportions. The major diastereoisomer of [PtCl(CHClCO2Et)(R,R-diop)] was readily separated by fractional crystallization, and its crystal structure revealed that the configuration at the alpha-carbon was R. This compound is configurationally stable for at least 14 d in CDCl3 solution as shown by P-31 NMR spectroscopy. Treatment of pure [PtCl(CHClCO2Et)(R,R-diop)] with S,S-skewphos led to exchange of diphosphines and thereby the assignment of the S configuration at the alpha-carbon of the major product of the reaction of [PtCl2(S,S-skewphos)] with ethyl diazoacetate. With the aim of optimizing the diastereoselectivity of the insertion reaction, the chiral diazo ester N2CHCO2R (R = R,R-menthyl) was used as the reagent but it was found that the diastereoselectivities were similar to those with N2CHCO2Et. The highest diastereoselectivities (up to 7:1) were obtained with N2CHCOPh.

  DOI：

  10.1021/om00059a062
• 作为产物：
  描述：

  bis(benzonitrile)dichloroplatinum(II) 、 (2S,4S)-(-)-2,4-双(二苯基磷)戊烷 以 苯 为溶剂， 以95%的产率得到PtCl2{(-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane}
  参考文献：
  名称：

  Temperature dependence of the asymmetric induction in the PtCl(SnCl3)[(−)-(2S,4S)-2,4-bis(diphenylphosphino)pentane]-catalyzed enantioselective hydroformylation reaction

  摘要：

  DOI：

  10.1016/0022-328x(88)80383-8
• 作为试剂：
  描述：

  苯乙烯 、 一氧化碳 在 PtCl2{(-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane} 、 氢气 、 tin(ll) chloride 作用下， 以 甲苯 为溶剂， 100.0 ℃ 、8.0 MPa 条件下， 反应 3.0h， 以7%的产率得到
  参考文献：
  名称：

  4-取代基对PtCl（SnCl 3）[（2 S， 4 S）-BDPP] 4-取代苯乙烯的不对称加氢甲酰化中对映选择性逆转的影响

  摘要：

  在原位催化剂存在下，由PtCl（SnCl 3）[（2 S，4 S）-BDPP]和氯化锡（II）形成的4-取代苯乙烯的不对称加氢甲酰基化的对映选择性受到反应的影响温度。支链醛区域异构体的S和R对映异构体的优选形成形式（2a – g分别在低温和​​高温下观察到。苯乙烯的对位取代基的电子给体或电子受体性质与对映选择性的变化，特别是与对映选择性的逆转温度相关。Pt支链烷基中间体形成的可逆性，导致相应的2-芳基丙醛的R和S对映体，取决于Hammett常数。通过简单的烯烃加合物[HPt（PH 3）2（烯烃）（SnCl 3），通过量子化学方法研究了对位取代基的电子效应。）]。在对位取代基常数和铂原子核的静电势之间发现极好的线性相关性。在Pt的配位范围内，其他原子也建立了相同的良好相关性。

  DOI：

  10.1021/om401104g

文献信息

• Novel diphosphine platinum cations: NMR and M�ssbauer spectra and catalytic studies
  作者：T KEGL

  DOI：10.1016/0022-328x(95)05630-8

  日期：1996.1

  has been investigated by NMR spectroscopy. [Pt(diphosphine) (PMe3)2]2+, [Pt(diphosphine)2]2+ and [Pt((S,S)-bdpp)((S,S)-chiraphos)]2+ cations have been characterized by 31P NMR and conductivity measurements. The presence of tin(II) chloride promotes the formation of the complex cations. Evidence for coordination of the diphosphine in monodentate mode has benn obtained by NMR spectroscopy. The platinum

  已经通过NMR光谱研究了PtCl 2（二膦）与单和​​二齿膦的反应。[Pt（二膦）（PMe 3）2 ] 2 +，[Pt（二膦）2 ] 2+和[Pt（（S，S）-bdpp）（（S，S）-chiraphos）] 2+阳离子已被以31为特征P NMR和电导率测量。氯化锡（II）的存在促进了复合阳离子的形成。通过NMR光谱已经获得了在单齿模式下二膦配位的证据。具有铂-锡键和离子的复合物用的SnCl铂物种3 -的抗衡离子可以容易地通过进行区分119的Sn穆斯堡尔谱。与[PT（（苯乙烯的不对称氢甲酰化小号，小号）-bdpp）2 ] 2+（的SnCl 3 - ）2作为催化剂前体，得到化学疗法，区域选择性和对映选择性从与所述共价氯铂酸获得的那些不同的（的SnCl 3）（（S，S）-bdpp）作为催化剂前体。
• Halogen Exchange in Platinum−Phosphine−Tin(II) Halide Systems. Characterization of the Novel PtI(SnCl₃)[(2<i>S</i>,4<i>S</i>)-2,4-bis(diphenylphosphino)pentane] Complex
  作者：Edit Farkas、László Kollár、Massimo Moret、Angelo Sironi

  DOI：10.1021/om9509406

  日期：1996.3.5

  The investigation of the PtCl2(diphosphine) + SnI2 and PtI2(diphosphine) + SnCl2 systems of catalytic importance (where diphosphines are 2,3-bis(diphenylphosphino)butane and 2,4-bis(diphenylphosphino)pentane) by NMR in solution has been carried out. Novel PtI(SnCl3)(diphosphine) and PtI(SnCl2I)(diphosphine) complexes were formed as a consequence of the halide exchange reaction. The selective formation

  通过以下方法研究具有催化重要性的PtCl 2（二膦）+ SnI 2和PtI 2（二膦）+ SnCl 2系统（其中二膦为2,3-双（二苯基膦基）丁烷和2,4-双（二苯基膦基）戊烷）溶液中已进行NMR。由于卤化物交换反应，形成了新的PtI（SnCl 3）（二膦）和PtI（SnCl 2 I）（二膦）配合物。在PtCl 2 [2，4-双（二苯基膦基）戊烷]与0.5 SnCl 2和0.5 SnI 2的反应中观察到PtI（SnCl 3）[2,4-双（二苯基膦基）戊烷]的选择性形成。铂（SnCl 3）[2，4-双（二苯基膦基）戊烷]是第一种包含手性螯合二膦和SnCl 3配体的铂配合物，通过X射线衍射对其结构进行了表征。
• Homo- and heterometallic chiral dynamic architectures from allyl–palladium(<scp>ii</scp>) building blocks
  作者：Montserrat Ferrer、Albert Gallen、Manuel Martínez、Mercè Rocamora、Rakesh Puttreddy、Kari Rissanen

  DOI：10.1039/d1dt03706d

  日期：——

  [M(P–P)*(H2O)2]2+ building blocks in a 1 : 1 molar ratio. The supramolecular assemblies thus prepared [Pd(η3-2-Me-C3H4)}2(4-PPh2py)4M(P–P)*}2](CF3SO3)6 (M = Pd, Pt) have been fully characterised by multinuclear NMR spectroscopy and MS spectrometry. The structures display remarkable differences on their dynamic behaviour in solution that depend on the lability and thermodynamic strength of M–py bonds. The

  含有烯丙基钯和 Pd(P-P)*} 或 Pt(P-P)*} 光学纯部分 (P-P* = (2S,3S)- O-异亚丙基-2,3-二羟基-1,4-双(二苯基膦基)丁烷(( S , S )-DIOP)和( 2S , 4S )-2,4-双(二苯基膦基)戊烷(( S , S )-BDPP)) 由[Pd(η 3 -2-Me-​​C 3 H 4 )(4-PPh 2 py) 2 ] +和[M(P-P)*( H 2 O) 2 ] 2+1 : 1 摩尔比的结构单元。由此制备的超分子组装体[Pd(η 3 -2-Me-​​C 3 H 4 )} 2 (4-PPh 2 py) 4 M(P-P)*} 2 ](CF 3 SO 3 ) 6(M = Pd, Pt) 已通过多核 NMR 光谱法和 MS 光谱法进行了充分表征。这些结构在溶液中的动态行为表现出显着差异，这取决于 M-py 键的不稳定性和热力学强度。所获得的新金属大环化合物的结构特征也已通过
• Kegl, Tamas; Kollar, Laszlo; Radics, Lajos, Inorganica Chimica Acta, 1997, vol. 265, # 1-2 PART II, p. 249 - 254
  作者：Kegl, Tamas、Kollar, Laszlo、Radics, Lajos

  DOI：——

  日期：——
• Highly stereospecific carbene insertions into platinum–halide bonds. Crystal structure of [PtCl(S-CHClSiMe₃)(S,S-Ph₂PCHMeCH₂CHMePPh₂)]
  作者：Paola Bergamini、Emiliana Costa、A. Guy Orpen、Christian Ganter、Paul G. Pringle

  DOI：10.1039/dt9940000651

  日期：——

  Trimethylsilyldiazomethane reacted with [PtX2L2] [X = Cl, Br or I; L2 = cycloocta-1,5-diene (cod) or Ph2P(CH2)nPPh2 where n = 1-4] to give the corresponding [PtX(CHXSiMe3)L2] as a racemic mixture in high yields. The cod ligands in [PtX(CHXSiMe3)(cod)] were readily displaced by diphosphines. When optically active complexes [PtX2L2] [X = Cl, Br or I; L2 = (2S,3S)-2,3-bis(diphenylphosphino)butane, (2S,4S)-2,4-bis(diphenylphosphino)pentane (S,S-skewphos) or (4R,5R)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane] were treated with trimethylsilyldiazomethane the products [PtX(CHXSiMe3)L2] were mixtures of diastereoisomers in different proportions ranging from 1:1 to 15:1. The major diastereoisomer of (PtCl(CHClSiMe3)(S,S-skewphos)] was readily separated by fractional crystallisation and its crystal structure revealed that the configuration at the alpha-carbon was S. This compound is configurationally stable for at least 14 d in CDCl3 solution as shown by P-31 NMR spectroscopy. The high diastereoselectivities obtained in some of the reactions may originate from steric effects.