Pd(Me)2(1,3-bis(diphenylphosphino)propane) | 113530-46-4

• 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: Pd(Me)2(1,3-bis(diphenylphosphino)propane)
• 英文别名: cis-dimethylbis(PPh2C3H6PPh2)palladium(II)；PdMe₂(dppp)；(1,3-bis(diphenylphosphino)propane)palladium(methyl)2；[Pd(CH3)2(1,3-bis-(diphenylphosphino)propane)]；[(dppp)Pd(CH3)2]；Carbanide;3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+)
• CAS: 113530-46-4
• 化学式: C₂₉H₃₂P₂Pd
• 分子量: 548.941
• InChiKey: KQGODIPJIYEROR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.54
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Pd(Me)2(1,3-bis(diphenylphosphino)propane) 、 2-烯丙基酚 以 乙醚 为溶剂， 以86%的产率得到Pd(Me)(1,3-bis(diphenylphosphino)propane)(2-allylphenolate)
  参考文献：
  名称：

  Synthesis and structure of methylpalladium(II) and -platinum(II) complexes with 2-allylphenoxido ligands, trans-PdMe(O6H4CH2CHCH2-o)(PR3)2 (R=Me, Ph) and PtMe(η1-O, η2-C,C-OC6H4CH2CHCH2-o)(PMe3). Simple O-coordination and chelating coordination depending on the metal center and auxiliary phosphine ligand

  摘要：

  Reactions of cis-PdMe2L2 (L = PMe3, PPh3, 0.5 dppp [dppp = Ph2P(CH2)(3)PPh2]) with equimolar 2-allylphenol afford the new complexes PdMe(OC6H4CH2CH=CH2-o)L2 (1: L = PMe3; 2: L = PPh3; 3: L = 0.5 dppp) in moderate to high yields. Addition of 2,2,2-trifluoro-1-phenylethanol to equimolar 1 results in formation of trans-PdMe(O6H4CH2CH=CH2-o)(PMe3)(2) . (HOCH(CF3) Ph), (4) which has been characterized by X-ray crystallography and NMR spectroscopy. Complex 4 contains O-H ... O hydrogen bonding between the allylphenoxido ligand and associated alcohol (O ... O = 2.635(6) Angstrom). The platinum complex PtMe(OC6H4CH2CH=CH2-o)(dppp), (5) is obtained from the alkoxido ligand exchange reaction of PtMe(OCH(CF3)(2))(dppp) with 2-allylphenol. Similar reaction of cis-PtMe(OR)(PMe3)(2) with equimolar 2-allylphenol at room temperature gives trans-PtMe(OC6H4CH2CH=CH2-o)(PMe3)(2) (6) in 55% yield. In contrast, reaction of cis-PtMe(OCH(CF3)(2))(PMe3)(2) . (HOCH(CF3)(2)) with excess 2-allylphenol at room temperature gives a mixture of 6 and PtMe(eta(1)-O, eta(2)-C, C-OC6H4CH2CH=CH2-o)(PMe3) (7) which are isolated in 16 and 28% yields, respectively. The isolated complex 7 has been characterized by NMR spectroscopy using several pulse techniques and X-ray analysis. The molecule has a distorted square-planar coordination around the metal center. The olefinic group in 2-allylphenoxido ligand is coordinated to the Pt center in a perpendicular fashion to the coordination plane. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00780-8
• 作为产物：
  描述：

  (N,N,N',N'-tetramethylethylenediamine)dimethylpalladium(II) 、 1,3-双(二苯基膦)丙烷 以 丙酮 为溶剂， 以77%的产率得到Pd(Me)2(1,3-bis(diphenylphosphino)propane)
  参考文献：
  名称：

  (1,3-双(二苯基膦)丙烷)Pd(II)中心迁移插入反应的动力学研究及其与乙烯和一氧化碳交替共聚的关系

  摘要：

  已经检查了与乙烯和 CO 通过高活性（dppp）Pd（II）基催化剂共聚相关的三个迁移插入过程的定量细节。在低温下生成并通过 1H、13C 和 31P NMR 光谱表征的阳离子 Pd(II) 中间体包括 (dppp)Pd(C2H4)(R)+ (R = -CH3, -CH2CH3)、6 和 7；(dppp)Pd(CO)(R)+ (R = -CH3, -CH2CH3)，8和11；和 (dppp)Pd(C2H4)(COCH3)+, 13. 对这些物种的迁移插入反应的动力学研究确定了以下活化参数：6(ΔG⧧ = 16.6(1) kcal/mol (-45.6 °C)， ΔH⧧= 15.2(7) kcal/mol, ΔS⧧ = −6.2(2.9) eu), 7(ΔG⧧ = 16.3(1) kcal/mol (-33.7 °C), ΔH⧧ = 15.9(8) kcal/ mol, ΔS⧧ = -1.6(3

  DOI：

  10.1021/ja994251n
• 作为试剂：
  描述：

  1-辛炔 、 亚磷酸二甲酯 在 Pd(Me)2(1,3-bis(diphenylphosphino)propane) 作用下， 以 neat (no solvent) 为溶剂， 反应 5.0h， 以98%的产率得到dimethyl 1-octen-2-yl-phosphonate
  参考文献：
  名称：

  钯催化炔烃的氢磷酸化：一般性和机理

  摘要：

  我们对钯催化的炔烃与 P(O)-H 化合物（即 H-膦酸盐、H-次膦酸盐、仲氧化膦和次膦酸）的一般性、范围、局限性和机理进行了全面研究）。对于 H-膦酸酯，Pd/dppp 是最好的催化剂。具有多种官能团的芳香族和脂肪族炔烃均适用于以高产率和高区域选择性生产马尔可夫尼科夫加合物。芳香族炔烃比脂肪族炔烃显示出更高的反应性。末端炔烃比内部炔烃反应更快。空间拥挤的 H-膦酸盐不喜欢添加。对于 H-次膦酸盐和仲氧化膦，Pd/dppe/Ph2P(O)OH 是首选催化剂，这导致马尔科夫尼科夫加合物的高度区域选择性形成。以Pd(PPh3)4为催化剂，将次膦酸加到末端炔烃上，得到相应的Markovnikov加合物。次膦酸、膦酸及其单酯不适用于这种钯催化的氢磷酸化。机理研究表明，(RO)2P(O)H 与末端炔烃反应，就像布朗斯台德酸一样，通过氢化钯反应选择性地生成 α-烯基钯中间体。另一方面，Ph(RO)P(O)H

  DOI：

  10.1021/jacs.8b00550

文献信息

• Bond Angle Effects on the Migratory Insertion of Ethylene and Carbon Monoxide into Palladium(II)−Methyl Bonds in Complexes Bearing Bidentate Phosphine Ligands
  作者：John Ledford、C. Scott Shultz、Derek P. Gates、Peter S. White、Joseph M. DeSimone、Maurice Brookhart

  DOI：10.1021/om010489k

  日期：2001.12.1

  (P−P)Pd(CH3)(OEt2)+BAr‘4- complexes (2) have been prepared via protonation of (P−P)PdMe2 (1), where P−P = cis-1,2-bis(diphenylphosphino)ethylene (a, dppee), 1,2-bis(diphenylphosphino)benzene (b, dpbz), 1,2-bis(diphenylphosphino)ethane (c, dppe), 1,2-bis(dimethylphosphino)ethane (d, dmpe), 1,3-bis(diphenylphosphino)propane (e, dppp), 1,3-bis(diisopropylphosphino)propane (f, dippp), 1,4-bis(diphenylphosphino)butane (g

  不稳定的（P-P）的Pd（CH 3）（OET 2）+ BAR” 4 -复合物（2）已通过（P-P）PDME的质子化制备2（1），其中，P-P =顺式-1， 2-双（二苯基膦基）乙烯（a，dppee），1,2-双（二苯基膦基）苯（b，dpbz），1,2-双（二苯基膦基）乙烷（c，dppe），1,2-双（二甲基膦基） ）乙烷（d，dmpe），1,3-双（二苯基膦基）丙烷（e，dppp），1,3-双（二异丙基膦基）丙烷（f，dippp），1,4-双（二苯基膦基）丁烷（g，dppb）和Ar’＝ 3，5-（CF 3）2 C 6 H 3。原位生成不稳定的复合物2d（PP = dmpe）。报告了1e和2e - g的X射线结构。在−90°C的CH 2 Cl 2中用CO处理2a - g，得到（P-P）Pd（CH 3）（CO）+络合物3a - g。壁垒洄游插入3A -克用顺序确定为：  3F（dippp）≈ 3克（DPPB）<
• The insertion of sulfur dioxide into palladium–methyl bonds: the synthesis and X-ray crystal structure of an unusual [(dppp)PdOS(Me)O]2[BAr′4]2 dimer
  作者：Derek P. Gates、Peter S. White、Maurice Brookhart

  DOI：10.1039/a905993h

  日期：——

  palladium(II)–methyl bond of [(dppp)Pd(Me)(OEt2)]BAr′4 [Ar′ = C6H3(CF3)2-3,5] to yield a unique dimeric eight-membered palladacycle was followed by NMR spectroscopy, and the product characterised by X-ray crystallography.

  二氧化硫迁移插入 [(dppp)Pd(Me)(OEt2)]BAr'4 [Ar' = C6H3(CF3)2-3,5] 的钯(II)-甲基键中，产生独特的二聚体八元钯环后进行核磁共振光谱分析，产物通过 X 射线晶体学进行表征。
• Synthesis of the Elusive (R₃P)₂MF₂ (M = Pd, Pt) Complexes
  作者：Anette Yahav、Israel Goldberg、Arkadi Vigalok

  DOI：10.1021/ja0377753

  日期：2003.11.1

  previously unknown palladium(II) and platinum(II) difluoro phosphine complexes are described. These complexes can be obtained either via a halide metathesis reaction with AgF in dichloromethane or by reacting the corresponding dimethyl complexes with XeF2. While the Pt(II) complexes can be prepared with both aryl- and alkyl-phosphine ligands, the stability of the Pd(II) complexes is limited to those

  描述了以前未知的钯 (II) 和铂 (II) 二氟膦配合物的合成和表征。这些配合物可以通过卤化物与 AgF 在二氯甲烷中的复分解反应或通过相应的二甲基配合物与 XeF2 反应获得。虽然 Pt(II) 配合物可以用芳基和烷基膦配体制备，但 Pd(II) 配合物的稳定性仅限于那些具有顺式取向的三烷基膦配体。
• Ozawa, Fumiyuki; Yamamoto, Akio, Nippon Kagaku Kaishi/Journal of the Chemical Society of Japan
  作者：Ozawa, Fumiyuki、Yamamoto, Akio

  DOI：——

  日期：——
• Synthesis and structure of methylpalladium(II) and -platinum(II) complexes with 2-allylphenoxido ligands, trans-PdMe(O6H4CH2CHCH2-o)(PR3)2 (R=Me, Ph) and PtMe(η1-O, η2-C,C-OC6H4CH2CHCH2-o)(PMe3). Simple O-coordination and chelating coordination depending on the metal center and auxiliary phosphine ligand
  作者：Yong-Joo Kim、Jae-Young Lee、Kohtaro Osakada

  DOI：10.1016/s0022-328x(97)00780-8

  日期：1998.5

  Reactions of cis-PdMe2L2 (L = PMe3, PPh3, 0.5 dppp [dppp = Ph2P(CH2)(3)PPh2]) with equimolar 2-allylphenol afford the new complexes PdMe(OC6H4CH2CH=CH2-o)L2 (1: L = PMe3; 2: L = PPh3; 3: L = 0.5 dppp) in moderate to high yields. Addition of 2,2,2-trifluoro-1-phenylethanol to equimolar 1 results in formation of trans-PdMe(O6H4CH2CH=CH2-o)(PMe3)(2) . (HOCH(CF3) Ph), (4) which has been characterized by X-ray crystallography and NMR spectroscopy. Complex 4 contains O-H ... O hydrogen bonding between the allylphenoxido ligand and associated alcohol (O ... O = 2.635(6) Angstrom). The platinum complex PtMe(OC6H4CH2CH=CH2-o)(dppp), (5) is obtained from the alkoxido ligand exchange reaction of PtMe(OCH(CF3)(2))(dppp) with 2-allylphenol. Similar reaction of cis-PtMe(OR)(PMe3)(2) with equimolar 2-allylphenol at room temperature gives trans-PtMe(OC6H4CH2CH=CH2-o)(PMe3)(2) (6) in 55% yield. In contrast, reaction of cis-PtMe(OCH(CF3)(2))(PMe3)(2) . (HOCH(CF3)(2)) with excess 2-allylphenol at room temperature gives a mixture of 6 and PtMe(eta(1)-O, eta(2)-C, C-OC6H4CH2CH=CH2-o)(PMe3) (7) which are isolated in 16 and 28% yields, respectively. The isolated complex 7 has been characterized by NMR spectroscopy using several pulse techniques and X-ray analysis. The molecule has a distorted square-planar coordination around the metal center. The olefinic group in 2-allylphenoxido ligand is coordinated to the Pt center in a perpendicular fashion to the coordination plane. (C) 1998 Elsevier Science S.A. All rights reserved.