Bis[2-di(propan-2-yl)phosphanyl-4-methylphenyl]azanide;chloropalladium(1+) | 666856-96-8

• 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-di(propan-2-yl)phosphanyl-4-methylphenyl]azanide;chloropalladium(1+)
• CAS: 666856-96-8
• 化学式: C₂₆H₄₀ClNP₂Pd
• 分子量: 570.431
• InChiKey: UTOGGRAQQBUMNY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.18
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  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
• 作为产物：
  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

文献信息

• Redox Communication between Two Diarylamido/Bis(phosphine) (PNP)M Moieties Bridged by Ynediyl Linkers (M = Ni, Pd, Pt)
  作者：Cheng-Han Yu、Xin Yang、Xiaozhou Ji、Chen-Hao Wang、Qingheng Lai、Nattamai Bhuvanesh、Oleg V. Ozerov

  DOI：10.1021/acs.inorgchem.0c01281

  日期：2020.7.20

  communication and delocalization was determined to be Pd < Ni ≤ Pt. On the Robin–Day scale, compounds 6M can be assigned class I for M = Pd and class II for M = Ni, Pt. Complex 3Pd also falls into class II, while 3Ni and 3Pt may be viewed as borderline class II/III cases. It is likely that the communication in the Ni systems has the advantage of the smaller size of Ni, resulting in a greater physical proximity

  已经准备了一系列一般类型（PNP）M– [连接基] –M（PNP）的双核同双金属配合物（M = Ni，Pd，Pt； PNP =双芳基/双（膦）钳型配体； - [接头] - =-C≡C-，-C≡CC≡C-，-C≡CC 6 H ^ 4 C≡C-）。每个（PNP）M位点都可以被一个电子氧化，这项工作报告了根据两个氧化还原位点之间的连通性和单氧化阳离子中离域度的混合价行为的研究。使用循环伏安法，UV-vis-NIR和EPR光谱，X射线晶体学和DFT计算来评估这些化合物。具有最长检验接头的复合物（PNP）Ni–C≡CC 6 H 4 C≡C–Ni（PNP）（9Ni），则在氧化还原站点之间未显示可辨别的通信。与-C≡C–接头类似物（PNP）M–C≡C–M（PNP）相比，同双金属配合物（PNP）M–C≡CC≡C–M（PNP）（6M）表现出较低的通讯度）（3M）。在这两个子集中的每个子集中，通信和离域的相对程度确定为Pd
• 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
• 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。
• N−C Cleavage in Pincer PNP Complexes of Palladium
  作者：Lei Fan、Lin Yang、Chengyun Guo、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/om049651k

  日期：2004.9.1

  Several new N-methylated diarylamine-based PNP pincer ligands have been prepared. The synthesis of these ligands is modular and allows incorporation of a variety of substituents that change the solubility and the stereoelectronic properties of the ligand as well as allow for the introduction of a sensitive F-19 NMR spectroscopic probe. The reactions of PN(Me)P ligands with PdX2 (X = Cl, OAc) initially proceed with formation of an adduct, (PN(Me)P)PdX2, that may exist in either the neutral or the ionic forms. These adducts are unreactive in the case of PPh2-bearing ligands, but with the more donating PPr2i-bearing ligands, the adduct evolves into square planar (PNP)PdX with irreversible loss of MeX. Thus, the feasibility of cleavage of an unstrained N-C bond by Pd-II is demonstrated. The N-C cleavage is accelerated by decreasing the solvent polarity. The mechanism may involve either N-C oxidative addition or a nucleophilic attack (external or internal) of X- on the Me group of the N-bound PN(Me)P ligand.
• Comparison of the Electronic Properties of Diarylamido-Based PNZ Pincer Ligands: Redox Activity at the Ligand and Donor Ability Toward the Metal
  作者：Jillian J. Davidson、Jessica C. DeMott、Christos Douvris、Claudia M. Fafard、Nattamai Bhuvanesh、Chun-Hsing Chen、David E. Herbert、Chun-I Lee、Billy J. McCulloch、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/ic503062w

  日期：2015.3.16

  This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a cornbination of a phosphino and an iminyl (-CH=NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C-2v-symmetric PNP ligands with identical side -PR2 donors, (b) C-2-Symmetric PNP' ligands with different-PR2 side donors, and (c) PNN ligands containing a -PPr2 side donor. All of the ligands under study readily formed square-planar complexes of the types (PNZ)PdCl, (pNZ)Pd(OAc), and (PNZ)RhCO, where PNZ is the corresponding anionic tridentate pincer ligand. For select PNP ligands, (PNP)NiCl and (PNP)PtCl were also studied. The (PNZ)MCl complexes (M = Ni, Pd, Pt) underwent quasireversible oxidation in cyclic voltammetry experiments, Based on the close similarity of formal potentials for Pd, and Pt analogs, and based on the previous literature evidence, these oxidation events are ascribed primarily to the PNZ ligand, and the E-1/2 values can be used to compare the ease of oxidation of different ligands. A (PNP)PdCl complex containing methoxy substituents para- to the central nitrogen underwent two quasireversible oxidations. Two mono-oxidized complexes were isolated and structurally characterized in comparison to their neutral analog, revealing minimal changes in the bond distances and angles. Several other neutral complexes were also structurally characterized. The carbonyl stretching frequency in (PN-Z)RhCO complexes was used to gauge the donating ability of the various pincer ligands toward the metal. Comparison of E-1/2 values for (PNZ)PdCl and v(CO) values for (PNZ)RhCO revealed that the two are not consistently correlated across all the studied ligands and can be tuned to different degrees through judicious ligand alteration.