(bis(2-(i)Pr2P-4-Me-phenyl)amido)Pd(H) | 666856-98-0

• 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: (bis(2-(i)Pr2P-4-Me-phenyl)amido)Pd(H)
• 英文别名: (PNP)PdH
• CAS: 666856-98-0
• 化学式: C₂₆H₄₁NP₂Pd
• 分子量: 535.986
• InChiKey: LASOLRQWSWWNQZ-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：

  (bis(2-(i)Pr2P-4-Me-phenyl)amido)Pd(H) 在 CH₂Cl₂ 作用下， 以 氘代苯 为溶剂， 生成 Bis[2-di(propan-2-yl)phosphanyl-4-methylphenyl]azanide;chloropalladium(1+)
  参考文献：
  名称：

  N−H Cleavage as a Route to Palladium Complexes of a New PNP Pincer Ligand

  摘要：

  Pd halide and hydride complexes of a new PNP pincer ligand with a central diarylamido moiety can be prepared via N-H cleavage in a neutral amine / diphosphine PNP ligand. The solid-state structure of (PNP)PdCl shows a meridional PNP ligand about an approximately square-planar Pd center. (PNP)PdH hydrodehalogenates alkyl and certain aryl halides, while (PNP)PdX (X = Cl, I, H, OAc) complexes catalyze Heck coupling of ethyl acrylate with aryl halides.

  DOI：

  10.1021/om034151x
• 作为产物：
  描述：

  Bis[2-di(propan-2-yl)phosphanyl-4-methylphenyl]azanide;chloropalladium(1+) 在 NaBH₄ 作用下， 以 四氢呋喃 为溶剂， 生成 (bis(2-(i)Pr2P-4-Me-phenyl)amido)Pd(H)
  参考文献：
  名称：

  N−H Cleavage as a Route to Palladium Complexes of a New PNP Pincer Ligand

  摘要：

  Pd halide and hydride complexes of a new PNP pincer ligand with a central diarylamido moiety can be prepared via N-H cleavage in a neutral amine / diphosphine PNP ligand. The solid-state structure of (PNP)PdCl shows a meridional PNP ligand about an approximately square-planar Pd center. (PNP)PdH hydrodehalogenates alkyl and certain aryl halides, while (PNP)PdX (X = Cl, I, H, OAc) complexes catalyze Heck coupling of ethyl acrylate with aryl halides.

  DOI：

  10.1021/om034151x

文献信息

• Oxidative Addition of N−C and N−H Bonds to Zerovalent Nickel, Palladium, and Platinum
  作者：Oleg V. Ozerov、Chengyun Guo、Lei Fan、Bruce M. Foxman

  DOI：10.1021/om0493513

  日期：2004.11.1

  (PNP)MMe (9). The N−H oxidative addition reactions are more facile. Both the N−H and N-Me oxidative addition reactions are kinetically inhibited by liberated phosphines from the LnM0 starting material. Thermolysis of (PNP)MMe (9, M = Ni, Pd, Pt) in the presence of excess PPh3 does not lead to N−C reductive elimination, thus indicating irreversibility of the N−C oxidative addition.

  基于双（邻膦基芳基）胺亚结构的螯合型PNP配体的反应，其中包含NH（PN（H）P，1）或N-Me（PN（Me）P，2）中心部分与第10组配合物已被探索。与MCl 2（MCl 2 = NiCl 2，（COD）PdCl 2，（COD）PtCl 2，COD = 1,5-环辛二烯）的反应很容易进行，会丢失HCl或MeCl并形成（PNP）MCl（7）其中PNP是阴离子，子午酰胺基-PNP配体。（PNP）MeCl与MeMgCl烷基化得到（PNP）MMe（9），（PNP）MCl与过量的NaBH 4反应提供（PNP）MH（8）。（PNP）MH（8）化合物与CDCl 3反应以再生（PNP）MCl（7）。与M = Ni或Pd相比，M = Pt的转换7 → 8 → 7 → 9变慢。确定（PNP）PdH（8b-Pd）和（PNP）PdMe（9b-Pd）的固态结构。在任何一种结构中，Pd的周围环境都是近似正方形的平面
• Heterolytic splitting of H–X bonds at a cationic (PNP)Pd center
  作者：Lauren C. Gregor、Chung-Hsing Chen、Claudia M. Fafard、Lei Fan、Chengyun Guo、Bruce M. Foxman、Dmitry G. Gusev、Oleg V. Ozerov

  DOI：10.1039/b925265g

  日期：——

  The (PNP)PdOTf complex is a suitable synthetic equivalent of the [(PNP)Pd]+ fragment in reactions with various HX substrates. The [(PNP)Pd]+ fragment either simply binds HX molecules as L-type ligands (X = NH2, PCy2, imidazolyl) or heterolytically splits the H–X bond to produce [(PN(H)P)Pd–X]+ (X = H, CCR, SR). DFT calculations analyze the relative energetics of the two outcomes and agree with the experimental data. Calculations also allow to assess the unobserved Pd(IV) isomer [(PNP)Pd(H)2]+ and validate its unfavourability with respect to the Pd(II) isomer [(PN(H)P)PdH]+.

  在与各种 HX 底物的反应中，(PNP)PdOTf 复合物是[(PNP)Pd]+ 片段的合适合成等价物。(PNP)Pd]+片段要么像 L 型配体（X = NH2、PCy2、咪唑基）一样简单地与 HX 分子结合，要么异质裂解 HâX 键生成[(PN(H)P)PdâX]+（X = H、CCR、SR）。DFT 计算分析了两种结果的相对能量，结果与实验数据一致。通过计算还可以评估未观察到的 Pd（IV）异构体 [(PNP)Pd(H)2]+ 并验证其相对于 Pd（II）异构体 [(PN(H)P)PdH]+ 的不可取性。
• Addition of Ammonia, Water, and Dihydrogen Across a Single Pd−Pd Bond
  作者：Claudia M. Fafard、Debashis Adhikari、Bruce M. Foxman、Daniel J. Mindiola、Oleg V. Ozerov

  DOI：10.1021/ja0731571

  日期：2007.8.1

  photochemical conversion to a dimeric (PNP)Pd−Pd(PNP) complex with a single Pd−Pd bond. Dissociation of the dimer into monomeric (PNP)Pd species is kinetically accessible thermally and photochemically. (PNP)Pd−Pd(PNP) reacts with ammonia, water, and dihydrogen by adding the H−X bond of the substrate (X = NH2, OH, H) across the Pd−Pd bond. For ammonia, this represents a rare example of conversion of NH3

  钳形钯烷基配合物 (PNP)PdR 经历光化学转化为具有单个 Pd-Pd 键的二聚体 (PNP)Pd-Pd(PNP) 配合物。二聚体解离成单体 (PNP) Pd 物种可通过热和光化学动力学进行。(PNP)Pd-Pd(PNP) 通过在 Pd-Pd 键上添加底物的 H-X 键 (X = NH2, OH, H) 与氨、水和二氢反应。对于氨，这代表了通过双金属配合物将 NH3 转化为末端氢化物和酰胺配体的罕见例子。
• Net Heterolytic Cleavage of B–H and B–B Bonds Across the N–Pd Bond in a Cationic (PNP)Pd Fragment
  作者：Yanjun Zhu、Chun-Hsing Chen、Claudia M. Fafard、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/ic2001283

  日期：2011.9.5

  The use of weakly coordinating anions BAr4F (where Ar-F = 3,5-(CF3)(2)C6H3) and CB11H12 allows one to access clean reactions of the [(PNP)Pd](+) fragment (PNP = bis(2-(Pr2P)-Pr-i (4) over bar -Me-phenyl)amido) with the B-H bond in cate-cholborane (CatBH) and catecholdiboron (CatBBCat). In both cases, a net heterolytic cleavage of B H or B B takes place, fragment. The resultant products [(PN(BCat)P)PdH](+) (2) with the nitrogen atom of PNP being a recipient of a boryl and [(PN(BCat)P)PdBCat](+) (3) were isolated as either BAr4F or CB,,H,2 salts and fully characterized. They are susceptible to hydrolysis, with the B-N bond hydrolyzing selectively and rapidly at RT to give [(PN(H)P)PdH](+) (1) and [(PN(H)P)- PdBCat](+) (4). Notably, 4 and 2 are isomers, but they do not interconvert even under thermolysis at 90 degrees C. The Pd-B bond in 4 can be further hydrolyzed more slowly, to give 1. On the other hand, a Pd-B bond was formed from the Pd-H bond in 2 by reaction with excess CatBH (and evolution of H-2), producing 3.