2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-fluorophenyl]-4-fluoro-N-methylaniline | 779333-68-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-fluorophenyl]-4-fluoro-N-methylaniline
• CAS: 779333-68-5
• 化学式: C₂₅H₃₇F₂NP₂
• 分子量: 451.52
• InChiKey: UEFKRRGRRCXFDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-fluorophenyl]-4-fluoro-N-methylaniline 以 氘代二甲亚砜 、 硝基甲烷 为溶剂， 生成 N(F(C6H3)P(i-Pr)2)2PdCl
  参考文献：
  名称：

  N−C Cleavage in Pincer PNP Complexes of Palladium

  摘要：

  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.

  DOI：

  10.1021/om049651k
• 作为产物：
  描述：

  氯二异丙基膦 、 在 正丁基锂 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-fluorophenyl]-4-fluoro-N-methylaniline
  参考文献：
  名称：

  Comparison of the Electronic Properties of Diarylamido-Based PNZ Pincer Ligands: Redox Activity at the Ligand and Donor Ability Toward the Metal

  摘要：

  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.

  DOI：

  10.1021/ic503062w

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
• Competitive Activation of N−C and C−H Bonds of the PNP Framework by Monovalent Rhodium and Iridium
  作者：Wei Weng、Chengyun Guo、Claudia Moura、Lin Yang、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1021/om050346o

  日期：2005.7.1

  This work describes how reactions of oxidative addition of N−C and C−H bonds are in competition in the PNP-ligated Rh and Ir complexes. Iridium appears to have a higher preference than Rh for the C−H activation over the N−C activation, and the Ir C−H activated complexes are more kinetically stable than their Rh analogues. A new generation of a diarylamido-based PNP pincer is presented, a “tied” PNP

  这项工作描述了N-C和C-H键的氧化加成反应在PNP连接的Rh和Ir络合物中如何竞争。铱似乎比Rh具有更高的优先权，其CH活化作用优于Nc活化作用，并且Ir CH活化的络合物比Rh的类似物在动力学上更稳定。提出了新一代的基于二芳基酰胺的PNP钳，一种基于亚氨基二苄基亚结构的“并列” PNP配体1c。该配体被更明确地预定为以子午线，阴离子PNP方式与金属中心结合。结果，它的N-C裂解反应（导致阴离子PNP的络合物）比“未结合”的配体1a，b更快。结构证据表明，当受主原子构象的影响时，在供体原子上带有相同的取代基时，“并列”阴离子PNP钳形配体比“未并列”配体更大。“并列”的钳形配体还允许观察中心N-CH 3基团的CH键的激活产物，而“未并列”的配体未检测到。与“未结合”配体的NC氧化加成反应以固态以及在溶液中进行。据报道，固态N-C氧化加成反应比溶液反应具有更高的选择性，结果显着。通过同位素标记（2
• 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.