双[2-(二异丙基膦)-4-甲基苯基]胺 | 666856-94-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 双[2-(二异丙基膦)-4-甲基苯基]胺
• 英文名称: bis[2-(diisopropylphosphino)-4-methylphenyl]amine
• 英文别名: Bis[2-(di-i-propylphosphino)-4-methylphenyl]amine；2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanyl-4-methylphenyl]-4-methylaniline
• CAS: 666856-94-6
• 化学式: C₂₆H₄₁NP₂
• 分子量: 429.566
• InChiKey: OHWMYFBSMLPIRY-UHFFFAOYSA-N

物化性质

• 沸点：
  523.1±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  29
• 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：
  12
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 危险性防范说明：
  P501,P273,P202,P201,P264,P280,P302+P352,P308+P313,P337+P313,P305+P351+P338,P362+P364,P332+P313,P405
• 危险性描述：
  H315,H319,H341,H413
• 储存条件：
  存储条件：2-8°C，避光，惰性气体环境。

反应信息

• 作为反应物：
  描述：

  双[2-(二异丙基膦)-4-甲基苯基]胺 以 氘代苯 为溶剂， 生成
  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：

  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 双[2-(二异丙基膦)-4-甲基苯基]胺
  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
• 作为试剂：
  描述：

  1-萘甲醇 、 环己胺 在 magnesium nitride 、 双[2-(二异丙基膦)-4-甲基苯基]胺 、 cobalt(II) bromide 、 锌 作用下， 以 均三甲苯 为溶剂， 反应 24.0h， 以53%的产率得到N-(1-naphthalenylmethylene)cyclohexylamine
  参考文献：
  名称：

  原位生成的钴催化剂，用于醇和胺的脱氢偶联成亚胺

  摘要：

  用溴化钴（II），双[2-（二异丙基膦基）-4-甲基苯基]胺和金属锌开发了原位形成的钴催化剂。该催化剂介导醇和胺的无受体脱氢偶联成亚胺，并释放出氢气，该转化被用于由不同的醇和胺合成各种亚胺。用标记的底物研究了该机理，并且基于结果，钴（I）PNP配合物被认为是催化活性物质，其通过金属配体双功能途径从醇中提取氢气。

  DOI：

  10.1002/cctc.201900392

文献信息

• High-valent nitridorhenium(<scp>v</scp>) complexes containing PNP ligands: implications of ligand flexibility
  作者：Nikola S. Lambic、Roger D. Sommer、Elon A. Ison

  DOI：10.1039/c7dt03615a

  日期：——

  methylnitridorhenium complex 3 was found to react differently with CO and isocyanides, leading to the isolation of a Re(V) acyl complex 4 and an isocyanide adduct 6. Two parallel pathways were observed for the reaction of 3 with CO: (1) CO inserts into the Re–Me bond to afford 4, and (2) 3 isomerizes by distortion of the aryl backbone of the PNP ligand to afford the isomer 3′. This is followed by the

  描述了（PNP）Re（N）X（PNP = [2-P（CHMe 2）2 -4-MeC 6 H 3 ] 2 N，X = Cl和Me）配合物的合成。发现甲基氮化or络合物3与CO和异氰化物的反应不同，从而导致Re（V）酰基络合物4和异氰化物加合物6的分离。对于3与CO的反应，观察到两个平行的途径：（1）CO插入Re-Me键得到4，（2）3通过PNP配体的芳基骨架变形而异构化，得到异构体3'。随后3'与CO反应得到三羰基配合物5，其已被充分表征。3与2，6-二甲基苯基异氰化物的对比反应为拟议的异构化途径提供了进一步的支持。DFT（M06）的计算表明，在室温下无法将CNR插入Re-Me键（27.2 kcal mol -1）。取而代之的是，基材通过最易接近的面（即syn-氮键的同位基）添加到金属中心，得到6。提议将CO加到异构体3'中以与2，6-二甲基苯基异氰化物相似的机理进行。
• N–H cleavage as a route to new pincer complexes of high-valent rhenium
  作者：Alex J. Kosanovich、Wei-Chun Shih、Rodrigo Ramírez-Contreras、Oleg. V. Ozerov

  DOI：10.1039/c6dt03640f

  日期：——

  A novel PNN-type pincer ligand has been accessed via imine reduction with LiAlH4 to provide the phosphine diamino proligand, PNHNH (1). The ligand, 1, as well as PNHP can be metallated directly, via N–H cleavage, with L2ReOX2(OEt) precursors to access six-coordinate (PNP)ReOCl2 (2) and (PNNH)ReOX2 (3-Cl, X = Cl; 3-Br, X = Br) in good yield. 3-Cl and 3-Br undergo dehydrohalogenation upon treatment with

  一种新的PNN型钳式配体已通过使用LiAlH 4的亚胺还原得到，以提供膦二氨基配体PN H N H（1）。配体1和PN H P可以通过N–H裂解直接与L 2 ReOX 2（OEt）前体金属化，从而获得六配位（PNP）ReOCl 2（2）和（PNN H）ReOX 2（3-Cl，X ＝ Cl；3-Br，X ＝ Br）以良好的收率。3-Cl和3-Br经NEt 3处理后进行脱卤化氢反应，以优异的收率提供了五配位的膦/二酰胺PNN型化合物（PNN）ReOX（4-Cl，X = Cl; 4-Br，X = Br），以混合形式存在旋转异构体。在分别与HCl （aq）和PMe 3分别提供3-Cl和4-PMe 3的反应中，显示了这种去质子的可逆性和4-Cl的配位不饱和。用AgOAc，AgOTf或NaHBEt 3处理4-Cl导致形成（PNN）ReO（OAc）（4-OAc），（PNN）ReO（OTf）（4-OTf）
• PNP-Ligated Heterometallic Rare-Earth/Ruthenium Hydride Complexes Bearing Phosphinophenyl and Phosphinomethyl Bridging Ligands
  作者：Wylie W. N. O、Xiaohui Kang、Yi Luo、Zhaomin Hou

  DOI：10.1021/om401216v

  日期：2014.2.24

  reaction of rare-earth bis(alkyl) complexes containing a bis(phosphinophenyl)amido pincer (PNP), LnPNPiPr(CH2SiMe3)2 (1-Ln, Ln = Y, Ho, Dy), with ruthenium trihydride phosphine complexes, Ru(C5Me5)H3PPh3 and Ru(C5Me5)H3PPh2Me, gave the corresponding bimetallic Ln/Ru complexes bearing two hydride ligands and a bridging phosphinophenyl (μ-C6H4PPh2-κP:κC1, 2a-Ln) or a bridging phosphinomethyl ligand (μ-CH2PPh2-κP:κC

  稀土类双（烷基）含有双（phosphinophenyl）酰氨基钳形（PNP），LnPNP络合物的反应我镨（CH 2森达3）2（1-LN，Ln为Y，何，DY），钌三氢化膦配合物，钌（C 5我5）H 3 PPH 3和Ru（C 5我5）H 3 PPH 2我，得到相应的双金属LN / Ru配合物带有两个氢化物配位体和一个桥连phosphinophenyl（μ-C 6 ħ 4 PPH 2 -κ P：κ ç 1，图2a-LN）或桥连配位体膦（μ-CH 2 PPH 2 -κ P：κ Ç，2B-LN），分别。的反应图2a-Y与CO气体在1个大气压和在20℃下在甲苯d 8，得到复合图3a-Y ，其带有一个桥接配位体pseudooxymethylene（μ-OCH（ø -C 6 ħ 4）PPH 2 -κ P：κ Ò）和在Y /钌中心桥接氢化物配位体。由DFT方法计算研究表明，3A-Y形成于两个步骤：CO的第一协调（Δ
• Synthesis and characterization of unsaturated Manganese(I) and Rhenium(I) dicarbonyl complexes supported by an anionic PNP pincer
  作者：Alex J. Kosanovich、Wei-Chun Shih、Oleg V. Ozerov

  DOI：10.1016/j.jorganchem.2019.06.020

  日期：2019.10

  Syntheses of Re and Mn carbonyl complexes of the diarylamido/bis(phosphine) PNP pincer ligand are reported. The saturated (PNP)Re(CO)3 and (PNP)Mn(CO)3 react cleanly with HBr in acetic acid to undergo decarbonylation with concomitant addition of HBr across the N-M bond. The resultant (PNHP)MBr(CO)2 (M = Mn or Re) complexes can be dehydrobrominated with triethylamine to yield the unsaturated (PNP)M(CO)2

  报道了二芳基酰胺/双（膦）PNP钳型配体的Re和Mn羰基配合物的合成。饱和的（PNP）Re（CO）3和（PNP）Mn（CO）3在乙酸中与HBr干净反应，进行脱羰基化，同时在NM键上添加HBr。可以用三乙胺将所得的（PNHP）MBr（CO）2（M = Mn或Re）络合物脱氢溴化，得到不饱和的（PNP）M（CO）2。（PNP）Re（CO）2对CO具有高亲和力，并从（PNP）Mn（CO）3中提取CO 。
• Experimental and computational exploration of the dynamic behavior of (PNP)BF2, a boron compound supported by an amido/bis(phosphine) pincer ligand
  作者：Jessica C. DeMott、Panida Surawatanawong、Shoshanna M. Barnett、Chun-Hsing Chen、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1039/c1dt11172h

  日期：——

  The diarylamido/bis(phosphine) PNP pincer ligand (2-iPr2P-4-MeC6H3)2N has been evaluated as a scaffold for supporting a BF2 fragment. Compound (PNP)BF2 (6) was prepared by simple metathesis of (PNP)Li (5) with Me2SBF3. NMR spectra of 6 in solution are of apparent C2 symmetry, suggestive of a symmetric environment about boron. However, a combination of X-ray structural studies, low-temperature NMR investigations, and DFT calculations consistently establish that the ground state of this molecule contains a classical four-coordinate boron with a PNBF2 coordination environment, with one phosphine donor in PNP remaining “free”. Fortuitous formation of a single crystal of (PNP)BF2·HBF4 (7), in which the “free” phosphine is protonated, furnished another structure containing the same PNBF2 environment about boron for comparison and the two PNBF2 environments in 6 and 7 are virtually identical. DFT studies on several other diarylamido/bis(phosphine) pincer (PNP)BF2 systems were carried out and all displayed a similar four coordinate PNBF2 environment in the ground state structures. The symmetric appearance of the room-temperature NMR spectra is explained by the rapid interconversion between two degenerate four-coordinate, C1-symmetric ground-state forms. Lineshape analysis of the 1H and 19F NMR spectra over a temperature range of 180–243 K yielded the activation parameters ΔH‡ = 8.1(3) kcal mol−1 and ΔS‡ = −6.0(15) eu, which are broadly consistent with the calculated values. Calculations indicate that the exchange of phosphine donors at the boron center proceeds by an intrinsically dissociative mechanism.

  这项研究评估了二芳基胺基/双(膦)PNP钳形配体(2-iPr2P-4-MeC6H3)2N作为支撑BF2片段的骨架。通过(PNP)Li5)与Me2SBF3的简单复分解反应制备了化合物(PNP)BF2 (6)。6在溶液中的核磁共振谱表现出表观C2对称性,暗示硼周围环境对称。然而,X射线结构研究、低温核磁共振研究和DFT计算一致表明,该分子的基态包含一个经典的四配位硼,具有PNBF2配位环境,其中PNP中的一个膦供体保持"游离"状态。意外形成的(PNP)BF2·HBF4 (7)单晶(其中"游离"膦被质子化)提供了另一个含有相同PNBF2环境的结构用于比较,6和7中的两个PNBF2环境几乎完全相同。对其他几个二芳基胺基/双(膦)钳形(PNP)BF2体系进行的DFT研究表明,所有基态结构都显示类似的四配位PNBF2环境。室温核磁共振谱的对称性外观可以用两个简并的四配位、C1对称基态形式之间的快速互变来解释。在180-243 K温度范围内对1H和19F核磁共振谱的线型分析得到活化参数ΔH‡ = 8.1(3) kcal mol−1和ΔS‡ = −6.0(15) eu,这与计算值基本一致。计算表明,硼中心的膦供体交换通过本质上的解离机制进行。