2-bromo-N-(2-(diisopropylphosphaneyl)-4-methylphenyl)-4-methylaniline | 1346171-72-9

• 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: 2-bromo-N-(2-(diisopropylphosphaneyl)-4-methylphenyl)-4-methylaniline
• CAS: 1346171-72-9
• 化学式: C₂₀H₂₇BrNP
• 分子量: 392.319
• InChiKey: DFOUYQNISJWAEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.73
• 重原子数：
  23.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-bromo-N-(2-(diisopropylphosphaneyl)-4-methylphenyl)-4-methylaniline 在 正丁基锂 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 35.0h， 生成 2-[2-[[2-[2-di(propan-2-yl)phosphanyl-4-methylanilino]-5-methylphenyl]methylideneamino]ethyliminomethyl]-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-4-methylaniline
  参考文献：
  名称：

  桥式配体配体支持的双核钯配合物

  摘要：

  一系列双核配体，每个配体包含两个三齿钳制位点，它们基于一个中心的单阴离子芳基（C）供体，两侧是中性膦基（P）和亚氨基（N）供体，[（PCN）-（CH 2）n-（PCN） ]（1）或中央为单阴离子的氨基（N），两侧为中性膦（P）和亚氨基供体（N）[[（PNN）-（CH 2）n-（PNN）]（4）。所述金属化而得位点通过两个当量的缩合联米羟基苯甲醛或有目的地建立非对称二芳基胺[（H）N（2-C（O）H-4-ME-C 6 H ^ 3）（2-P（我Pr）2 -4-Me-C 6 H3）]（3）与伯α，ω-二胺（1,2-二氨基乙烷，n = 2； 1,4-二氨基丁烷，n = 4），它们同时构成了亚氨基臂并桥接了钳形核。然后将配体1和4用于合成中性的方形方形钯（II）配合物5和6 [[（PCN-C n）Pd 2 X 2，（PNN-C n）Pd 2 X 2 ; n = 2，4; X ＝ Cl，OAc，OTf

  DOI：

  10.1021/om2008056
• 作为产物：
  描述：

  4,4'-二甲基二苯胺 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 60.5h， 生成 2-bromo-N-(2-(diisopropylphosphaneyl)-4-methylphenyl)-4-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

• Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes
  作者：Chun-I Lee、Jessica C. DeMott、Christopher J. Pell、Alyson Christopher、Jia Zhou、Nattamai Bhuvanesh、Oleg V. Ozerov

  DOI：10.1039/c5sc02161h

  日期：——

  Following the report on the successful use of SiNN pincer complexes of iridium as catalysts for dehydrogenative borylation of terminal alkynes (DHBTA) to alkynylboronates, this work examined a wide variety of related pincer ligands in the supporting role in DHBTA. The ligand selection included both new and previously reported ligands and was developed to explore systematic changes to the SiNN framework

  继关于成功使用铱的 SiNN 钳形配合物作为末端炔烃 (DHBTA) 脱氢硼化为炔基硼酸盐的催化剂的报告之后，这项工作研究了各种相关钳形配体在 DHBTA 中的支持作用。配体选择包括新的和以前报道的配体，旨在探索 SiNN 框架（8-（2-二异丙基甲硅烷基苯基）氨基喹啉）的系统变化。令人惊讶的是，只有二芳基氨基/双（膦） PNP 系统显示出任何 DHBTA 反应性。筛选中使用的特定 PNP 配体（带有两个二异丙基膦基侧供体）显示 DHBTA 活性低于 SiNN。然而，利用 PNP 系统提供的配体优化机会，通过磷取代的变化导致发现了一种催化剂，其活性、寿命和范围远远超过了原始 SiNN 原型。在模型 PNP 系统中制备了几种 Ir 配合物，并作为催化循环中的潜在中间体进行了评估。其中，(PNP)Ir 二硼基络合物和硼基亚乙烯基络合物显示出催化能力较差，因此可能不是催化循环的一部分。
• Synthesis and characterization of rhodium, iridium, and palladium complexes of a diarylamido-based PNSb pincer ligand
  作者：Alex J. Kosanovich、Aldo M. Jordan、Nattamai Bhuvanesh、Oleg. V. Ozerov

  DOI：10.1039/c8dt02207k

  日期：——

  A new diarylmido-based pincer proto ligand (iPrPNHSbPh) with one –PPri2 and one –SbPh2 side donor has been synthesized. Three complexes of its amido form were prepared using standard metalation techniques: (iPrPNSbPh)PdCl, (iPrPNSbPh)RhCO, and (iPrPNSbPh)Ir(COE), where COE = cis-cyclooctene. These complexes were compared with their previously reported analogs incorporating a –PPh2 side donor in place

  合成了一种新的基于二芳基亚胺的钳型原配体（iPr PN H Sb Ph），该配体具有一个–PPr i 2和一个–SbPh 2侧供体。使用标准金属化技术制备了其酰胺形式的三种配合物：（iPr PNSb Ph）PdCl，（iPr PNSb Ph）RhCO和（iPr PNSb Ph）Ir（COE），其中COE =顺式环辛烯。将这些复合物与先前报道的掺入–PPh 2侧供体代替–SbPh的类似物进行了比较。2。根据Rh配合物的结构和IR光谱分析，–SbPh 2供体对金属的贡献较少，且反式影响较小。从–PPh 2到–SbPh 2的变化仅略微影响Pd配合物的氧化还原电势。（iPr PNSb Ph）Ir（COE）在末端炔烃（DHBTA）的脱氢硼化反应中比–PPh 2类似物被证明是一种速度更慢，选择性更低的催化剂。
• Unsymmetrical RPNPR′ pincer ligands and their group 10 complexes
  作者：Raymond B. Lansing、Karen I. Goldberg、Richard A. Kemp

  DOI：10.1039/c1dt10265f

  日期：——

  Two new unsymmetrical RPNPR′-type pincer ligands based on a bis(tolyl)amine framework have been synthesized and characterized by a variety of techniques, including X-ray crystallography. These ligands have been coordinated to Ni, Pd, and Pt precursors to provide a number of well-characterized group 10 halides. Conversion of these metal halides to metal hydrides was accomplished using borohydride reagents, or by direct interaction of the ligand with the zerovalent metal precursor. The insertion of oxygen into these hydrides in an attempt to prepare metal hydroperoxides has been examined; however, we were unable to obtain stable and isolable hydroperoxide species.

  我们合成了两种基于双（甲苯基）胺框架的新型非对称 RPNPRâ² 型钳形配体，并通过 X 射线晶体学等多种技术对其进行了表征。这些配体与镍、钯和铂前体配位后，产生了许多特征良好的第 10 族卤化物。利用硼氢化试剂或配体与零价金属前体的直接作用，可以将这些金属卤化物转化为金属氢化物。为了制备金属氢过氧化物，我们研究了在这些氢化物中加入氧气的方法；但是，我们无法获得稳定且可分离的氢过氧化物。
• Palladium complexes of a new phosphine-amido-siloxide pincer ligand with variable degrees of protonation
  作者：Jillian J. Davidson、C.M. Nagaraja、Chun-Hsing Chen、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1016/j.ica.2014.07.033

  日期：2014.10

  This manuscript describes the preparation of a new PN(H)SiO(H) pincer-type ligand that is based on the diarylamine backbone and links together phosphine, amine, and silanol donor sites. Treatment of PN(H)SiO(H) with Pd(acac)(2), (COD)PdCl2, or Pd(OAc)(2) resulted in the formation of (kappa(2)-PNSiO(H))P(acac) (3), (kappa(2)-PN(H)SiO(H))PdCl2 (4), and (kappa(3)-PNSiO(H))PdOAc (5), in which the supporting ligand displays different degrees of coordination and protonation. In complex 5, the PNSiO(H) ligand functions as a tridentate phosphine-amido-silanol pincer ligand, with additional strong hydrogen bonding between the silanol OH and one of the oxygens of the Pd-bound acetate. Complex 5 cleanly exchanged acetate for a triflate upon treatment with Me3SiOTf, yielding (kappa(3)-PNSiO(H))PdOTf (6). Analogous treatment with Me3SiCl did not lead cleanly to the expected (kappa(3)-PNSiO(H))PdCl (7), but instead ultimately to (kappa(2)-PN(H)SiO(SiMe3))PdCl2 (8). The dianionic PNSiO ligand was accessed by reactions of 5 with base in the presence of pyridine or PMe3 to give (kappa(3)-PNSiO)Pd(py) (9) and (kappa(3)-PNSiO)Pd(PMe3) (10), respectively. Solid-state structures of 5 and 9 were established by single-crystal X-ray diffractometry and revealed square-planar geometry about Pd with tridentate coordination of the pincer ligand. (C) 2014 Published by Elsevier B.V.