bis(2-diphenylphosphine-4-methylphenyl)amine | 1011473-19-0

• 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-diphenylphosphine-4-methylphenyl)amine
• 英文别名: bis(2-(diphenylphosphaneyl)-4-methylphenyl)amine；bis(2-diphenylphosphino-4-methylphenyl)amine；HN(2-PPh2-4-Me-C6H3)2；HN(C6H3(Me)PPh2)2；NH(2-PPh2-4-Me-C6H3)2；PNP(Ph)H；2-diphenylphosphanyl-N-(2-diphenylphosphanyl-4-methylphenyl)-4-methylaniline
• CAS: 1011473-19-0
• 化学式: C₃₈H₃₃NP₂
• 分子量: 565.634
• InChiKey: JJWMOPGQEAOTSL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(2-diphenylphosphine-4-methylphenyl)amine 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 双三氟甲烷磺酰亚胺银盐 作用下， 以 二氯甲烷 、 二氯甲烷-D2 、 水 、 正戊烷 为溶剂， 反应 2.25h， 生成
  参考文献：
  名称：

  氧化还原活性桥联PNP配体支持的双核金物种的受控互变促进配体到金的电子转移

  摘要：

  氧化还原非纯配体最近成为有趣的工具，可以与多种金属获得新的反应性。但是，黄金在这方面几乎被忽略了。在这里，我们报告了与金的配位领域中基于配体的氧化还原化学的一个罕见例子有关的机理研究。双核金属中心的混合价的Au我-Au III复杂1，通过单阴离子diarylamido-二膦配体PNP支持镨并用整体3个chlorido配体，通过经历银盐一系列复杂时卤化物夺取反应的或路易斯酸如镓三氯化物。最终Au I – Au I配合物2的形成需要Au构成的中间性我-Au我二聚体5和7以及独特的Au III -Au III复杂6，这两者在反馈环路中被相互转化。最后，氧化还原活性PNP配体的空前的邻位C-H活化通过配体-金属二电子转移产生咔唑基二膦衍生物PN * P Pr。这项工作表明，使用反应性配体支架时，金的氧化还原化学作用可能会大大扩展和修饰。

  DOI：

  10.1002/chem.201700360
• 作为产物：
  描述：

  bis(2-bromo-4-methylphenyl)amine 、 二苯基氯化膦 在 正丁基锂 、 盐酸 作用下， 生成 bis(2-diphenylphosphine-4-methylphenyl)amine
  参考文献：
  名称：

  Gallium and indium compounds supported by a [PNP] pincer ligand

  摘要：

  The new bis(phosphino) amido ligand, [MePNPPh], that incorporates (i) an ortho-tolylene linker between nitrogen and phosphorus and (ii) phenyl substituents on phosphorus, has been synthesized as its protonated derivative, [MePNPPh] H, via sequential treatment of (2-Br, 4-Me-C6H3)(2)NH with (i) (BuLi)-Li-n, (ii) Ph2PCl and (iii) HCl. Deprotonation of [MePNPPh]H with (BuLi)-Li-n in THF affords the lithium derivative which has been isolated as both mono and bis THF adducts, [MePNPPh]Li(THF) and [MePNPPh]Li(THF)(2). Treatment of [MePNPPh]Li(THF)(2) with GaCl3 and InX3 (X = Cl, Br, I) gives a series of [MePNPPh]MX2 complexes in which the [PNP] donor binds in a "T"-shaped manner and the metal has a distorted trigonal bipyramidal geometry. The reaction of [MePNPPh]Li(THF)(2) with "GaI" yields the Ga-Ga bonded complex [kappa(2)-MePNPPh](GaI)(GaI)[kappa(2)-MePNPPh] in which the [MePNPPh] ligand binds in a kappa(2)-P,N manner. The bis(phosphino) amine [MePNPPh]H may also serve as a ligand and treatment of [MePNPPh]H with GaBr3 affords [kappa(2)-{[MePNPPh]H}GaBr2][GaBr4], in which the [MePNPPh]H ligand coordinates in a kappa(2)-P,P manner such that the gallium adopts a tetrahedral geometry. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.07.064

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 reactivity of rhodium and iridium alkene, alkyl and silyl complexes supported by a phenyl-substituted PNP pincer ligand
  作者：Elisa Calimano、T. Don Tilley

  DOI：10.1039/b925856f

  日期：——

  and R = Et (17); M = Rh, R = Ph (18), Et (19) and Ph2Cl (20)) via Si–H oxidative addition. The JSiH coupling constants for rhodium complexes 18, 19 and 20 were determined to be ca. 35 Hz, while iridium complexes 16 and 17 exhibited coupling constants less than 10 Hz. X-Ray crystal structures of 16 and 18 reveal isostructural complexes featuring a trigonal bipyramidal geometry about iridium with a mer

  新的 铑 和 铱 苯基取代的PNP钳形配体支持的配合物 PNP Ph H合成了（HN（2-PPh 2 -4-Me-C 6 H 3）2）（1）。2当量的反应。的1与[（COD）IrCl] 2 提供了协调中心 [（PNP Ph H）Ir（COD）] Cl（2）特色氢 N–H基团与 氯化物阴离子，通过NMR光谱和X射线晶体学表征。1与的反应[（COE）2 IrCl] 2 或者 [（COE）2 RhCl] 2 在 苯 提供了多种复合物，包括 （PNP Ph H）MHCl 2 （M = 铱（4），M =铑（7））和（PNP）M（COE） （M = 铱（5），M =铑（8））。类型的烯烃配合物（PNP Ph）M（L） （M = 铱，L = 化学需氧量（3）及COE（5）; M =铑，L = COE（8）并且L =乙烯（9））是通过反应合成的。（PNP Ph）李与适当的氯化烯烃配合物。与硅烷的反应5，8或9所产生氢化硅烷配合物（PNP
• Pseudotetrahedral cobalt(<scp>ii</scp>) complexes with PNP-ligands showing uniaxial magnetic anisotropy
  作者：Yuan-Qi Zhai、Yi-Fei Deng、Yan-Zhen Zheng

  DOI：10.1039/c8dt01683f

  日期：——

  mononuclear pseudotetrahedral cobalt(II) complexes with the formula Co(PNP)X2, where X = Cl (1) or X = SCN (2) and PNP = bis(2-(diphenylphosphaneyl)-4-methylphenyl)amine, have been synthesised. Magnetic and high-frequency/field electron paramagnetic resonance (HF-EPR) spectroscopy and ab initio calculation studies reveal that both complexes show uniaxial magnetic anisotropy.

  两个具有式Co（PNP）X 2的单核拟四面体钴（II）配合物，其中X = Cl（1）或X = SCN（2）和PNP =双（2-（二苯基膦基）-4-甲基苯基）胺已合成。磁和高频/场电子顺磁共振（HF-EPR）光谱和从头算计算研究表明，两种配合物均显示出单轴磁各向异性。
• Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes
  作者：Long Yiu Tsang、Wei Bai、Lam Cheung Kong、Herman H. Y. Sung、Ian D. Williams、Guochen Jia

  DOI：10.1021/acs.organomet.4c00024

  日期：2024.4.22

  While alkyne metathesis reactions involving d0 carbynes (alkylidynes) are well documented, those involving well-defined non-d0 carbynes are still rare. This work reports the synthesis and alkyne metathesis activity of d2 Re(V) carbyne complexes supported by a [LXL]-type monoanionic [PNP]-pincer ligand, a [LLX]-type monoanionic [PNO]-pincer ligand, and a [ONOH]-bidentate ligand derived from the Schiff

  虽然涉及 d 0卡宾（亚烷基）的炔复分解反应已有充分记录，但涉及明确定义的非 d 0卡宾的反应仍然很少。这项工作报道了由[LXL]型单阴离子[PNP]-钳配体、[LLX]型单阴离子[PNO] -钳配体和[ON OH ]-二齿配体衍生自席夫碱2-[(2-羟基苯基)亚氨基甲基]苯酚。用双(2-二苯基膦基-4-甲苯基)胺(PNHP)和2 -(2-二苯基膦基-苯基)亚氨基甲基}苯酚(PNOH)处理Re(≡CCH 2 Ph)Cl 2 (PMePh 2 ) 3 ( 1 ) ) 在 NEt 3存在下分别产生钳形配合物 Re(iCCH 2 Ph)Cl(PMePh 2 )(PNP) ( 2 ) 和 Re(iCCH 2 Ph)Cl(PMePh 2 )(PNO) ( 3 ) 。席夫碱2-[(2-羟基苯基)亚氨基甲基]苯酚(HON OH )与Re(≡CCH 2 Ph)Cl 2 (PMePh 2 ) 3 ( 1 )反应得到席夫碱配合物Re(≡CCH
• 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.