Pd(η(2),η(2)-C6H10O)P(iPr)3 | 210691-21-7

• 英文名称: Pd(η(2),η(2)-C6H10O)P(iPr)3
• 英文别名: (iPr3P)Pd(η2,η2-C6H10O)；Pd(η²:η²-diallyl ether)(PⁱPr₃)
• CAS: 210691-21-7
• 化学式: C₁₅H₃₁OPPd
• 分子量: 364.804
• InChiKey: NJKGYOVLRYQKOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Pd(η(2),η(2)-C6H10O)P(iPr)3 、 四甲基二乙烯基二硅氧烷 以 not given 为溶剂， 生成 [Pd((η(2)-CH2CHSiMe2)2O)P(CH(CH3)2)3]
  参考文献：
  名称：

  Hepta-1,6-diene and diallyl ether complexes of palladium(0) and platinum(0):a route to L–M(alkene)2 complexes containing non-activated alkenes

  摘要：

  与 hepta-1,6-二烯和双烯醚反应，Pd⁰ 和 Pt⁰ 形成高度反应性的同配体二核 M₂(1,6-二烯)₃ 复合物，这些复合物被供体 L（例如 C₂H₄、膦类、磷酸酯、异氰基化合物）裂解，生成单核衍生物 L–M(1,6-二烯)；（Me₃P）Pd{(η²-CH₂CHCH₂)₂O} 的 X 射线结构已被确定。

  DOI：

  10.1039/a802381f
• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 以 乙醚 为溶剂， 生成 Pd(η(2),η(2)-C6H10O)P(iPr)3
  参考文献：
  名称：

  Hepta-1,6-diene and diallyl ether complexes of palladium(0) and platinum(0):a route to L–M(alkene)2 complexes containing non-activated alkenes

  摘要：

  与 hepta-1,6-二烯和双烯醚反应，Pd⁰ 和 Pt⁰ 形成高度反应性的同配体二核 M₂(1,6-二烯)₃ 复合物，这些复合物被供体 L（例如 C₂H₄、膦类、磷酸酯、异氰基化合物）裂解，生成单核衍生物 L–M(1,6-二烯)；（Me₃P）Pd{(η²-CH₂CHCH₂)₂O} 的 X 射线结构已被确定。

  DOI：

  10.1039/a802381f

文献信息

• 1,6-Diene Complexes of Palladium(0) and Platinum(0):  Highly Reactive Sources for the Naked Metals and [L−M⁰] Fragments
  作者：Jochen Krause、Günter Cestaric、Karl-Josef Haack、Klaus Seevogel、Werner Storm、Klaus-Richard Pörschke

  DOI：10.1021/ja983939h

  日期：1999.10.1

  1−12 react with donor ligands such as phosphanes, phosphites, or tBuNC to give isolated complexes of types L−M(1,6-diene) (13−41), which have also been prepared by other routes. In all complexes the metal centers are TP-3 coordinated: complexes 1−4 contain chelating and bridging 1,6-diene ligands, whereas the other complexes contain a chelating 1,6-diene ligand and an η2-a...

  配合物 (cod)MCl2 (M = Pd, Pt; cod = cis,cis-1,5-cyclooctadiene) 与 Li2(cot) (cot = cyclooctatetraene) 在 1,6-二烯/乙醚混合物 (1, 6-二烯 = 庚-1,6-二烯、二烯丙基醚、dvds (1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷)) 得到分离的均质双核 Pd0 和 Pt0 化合物 Pd2(C7H12)3 ( 1)、Pd2(C6H10O)3· (2'；2：Pd2( )3)、Pd2(dvds)3(3)和Pt2( )3(4)。当 1-4 用额外的 1,6-二烯处理时，M(1,6-二烯)2 (5-8) 型的同样均质但单核的衍生物和乙烯混合烯烃配合物 (C2H4)M(1,6 -二烯) (9-12) 在溶液中获得。配合物 1-12 与供体配体如膦、亚磷酸盐或 tBuNC
• Selective Alkene Insertion into Inert Hydrogen–Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes
  作者：Nobuyuki Komine、Ryo Ito、Hiromi Suda、Masafumi Hirano、Sanshiro Komiya

  DOI：10.1021/acs.organomet.7b00593

  日期：2017.11.13

  mono(phosphorus ligand)palladium(0) complexes catalyzed alkene insertions into hydrogen–tungsten bonds. These insertions using WHCp(CO)3 with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono(phosphorus ligand)mono(alkene)palladium(0) species

  孤立的单（磷配体）钯（0）​​络合物催化烯烃插入氢-钨键中。使用WHCp（CO）3与丙烯酸乙酯和富马酸二甲酯进行的这些插入操作顺利生成了相应的烷基钨络合物。涉及化学计量反应和DFT计算的动力学研究建议采取以下步骤：（i）形成单（磷配体）单（烯烃）钯（0）​​物种，（ii）金属氢化物与钯（0）的后续反应；（iii）将配位烯烃插入所得的氢化钯中，以及（iv）通过钯与烯烃的反应再生钯（0），从而在钯中心上的烷基与金属之间进行还原性消除，从而释放出烷基金属。
• A Dinuclear Palladium(I) Ethynyl Complex:  Synthesis, Structure, and Dynamics
  作者：Jochen Krause、Richard Goddard、Richard Mynott、Klaus-Richard Pörschke

  DOI：10.1021/om000765f

  日期：2001.5.1

  The reaction of Pd(eta (3)-C3H5)(2) with (PPr3)-Pr-i at -30 degreesC affords yellow crystals of the Pd-II complex ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)(eta (3)-C3H5) (1). At 20 degreesC 1 transforms into the dinuclear Pd-I complex ((Pr3P)-Pr-i)Pd)(2)(mu -C3H5)(2) (2) due to oxidative C-C coupling of two allyl groups with elimination of 1,5-hexadiene. Heating 1 or 2 in 1,6-heptadiene to 80 degreesC produces the Pd-0 complex ((Pr3P)-Pr-i)Pd(eta (2),eta (2)-C7H12) (3) (eta (3)-C3H5)PdCl}(2) reacts with (Pr3P)-Pr-i to give ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)Cl (4b), from which further derivatives ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)X (X = OSO2CF3 (4a), C drop CH (5a), CH3 (5b)) are obtained by replacement reactions. The mononuclear Pd-II-acetylide Sa and complex 3 combine to give the dinuclear Pd-I derivative ((Pr3P)-Pr-i)Pd}(2)(mu -C3H5)(mu (2)-eta (2)-C2H) (6). The Pd-Pd bond in 6 is unsymmetrically bridged by a pi -allyl and a sigma-pi -ethynyl group, as determined by X-ray structure analysis. The structures of 1, 4a,b, and 6 are dynamic in solution, with 1 undergoing an exchange of the binding modes of the pi- and sigma -coordinated allyl groups and 4a,b displaying a pi/sigma -allyl group rearrangement, and in 6 the C drop CH substituent oscillates in its pi -coordination from one Pd-I atom to the other.