tris(2-pyridyl)methane | 77429-58-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: tris(2-pyridyl)methane
• 英文别名: 2-(dipyridin-2-ylmethyl)pyridine
• CAS: 77429-58-4
• 化学式: C₁₆H₁₃N₃
• 分子量: 247.299
• InChiKey: KOGZGHWZQGNJAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tris(2-pyridyl)methane 在 4-叔丁基吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， 反应 0.25h， 生成 [(Py3CH)PdIV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OAc]
  参考文献：
  名称：

  A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers

  摘要：

  This report describes a detailed investigation of acetate-assisted C-H activation at Pd-IV centers supported by the tris(2-pyridyl)-methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following:, (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)Pd-IV(biphenyl)Cl-2)(+) occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.

  DOI：

  10.1021/ja401557m
• 作为产物：
  描述：

  三(2-吡啶基)甲基醇 在 氯化亚砜 、 三正丁基氢锡 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 tris(2-pyridyl)methane
  参考文献：
  名称：

  Strong Lewis acids derived from molybdenum and tungsten nitrosyls containing the tri-2-pyridylmethane ligand. Dynamic NMR studies of their adducts with aldehydes, ketones, and esters

  摘要：

  The doubly charged Lewis acid precursors [HC(py)3M(NO)2(CO)](SbF6)2 (M = Mo, W; HC(py)3 = tri-2-pyridylmethane) are conveniently synthesized by reaction of HC(py)3M(CO)3 and 2 equiv of NOSbF6. Facile loss of CO from the precursors generates the [HC(py)3M(NO)2](SbF6)2 Lewis acids. The Lewis acidity of the tungsten complex is greater than that of the molybdenum complex. With the H-1 NMR chemical shifts of bound crotonaldehyde as a qualitative assessment of relative acidity, the acidity of the tungsten species is comparable to that of BF3 and AlCl3, while that of the molybdenum species is similar to that of TiCl4. Analysis of the NMR spectra of the Lewis acid-organic carbonyl base adducts, which include the adducts of aldehydes, ketones, and esters, showed that eta-1-M(O = C) interactions dominate the chemistry. The barriers of rotation about the aldehyde C1-C2 bonds in the p-anisaldehyde adducts of the molybdenum and tungsten species were measured to be 12.8 and 13.7 kcal/mol, respectively, which are significantly higher than that for the free p-anisaldehyde. The exchange behavior between the E and Z isomers of the acetate adducts could be observed on the NMR time scale. The E to Z interconversion barriers of 12.2 +/- 0.1 and 12.3 +/- 0.1 kcal/mol for the methyl acetate and ethyl acetate complexes, respectively, were calculated from the results of variable-temperature proton NMR experiments. The free energy differences between the E and Z conformers of the methyl acetate and ethyl acetate adducts are 1.27 +/- 0.01 and 0.96 +/- 0.01 kcal/mol at 229 K, respectively.

  DOI：

  10.1021/ja00005a021

文献信息

• Synthesis of new copper(<scp>i</scp>) complexes with tris(2-pyridyl) ligands. Applications to carbene and nitrene transfer reactions
  作者：Julio Pérez、Dolores Morales、Luis A. García-Escudero、Héctor Martínez-García、Daniel Miguel、Pablo Bernad

  DOI：10.1039/b812604f

  日期：——

  New copper(I) complexes with tris(2-pyridyl)methane (TPC), tris(2-pyridyl)methoxymethane (TPM) and tris(2-pyridyl)amine (TPN) ligands have been synthesized and characterized, including structural determinations by X-ray diffraction of some examples. Their activity as catalysts in carbene and nitrene transfer reactions was studied.

  合成并表征了具有三（2-吡啶基）甲烷（TPC），三（2-吡啶基）甲氧基甲烷（TPM）和三（2-吡啶基）胺（TPN）配体的新型铜（I）配合物，包括通过X射线衍射的一些例子。研究了它们在卡宾和氮烯转移反应中作为催化剂的活性。
• Structures and spectra of bis-tripodal iron(II) chelates, [FeL2]2+, where L = tris(pyrazol-1-yl)methane, tris(pyridin-2-yl)methane, bis(pyrazol-1-yl)(pyridin-2-yl)methane and tris(pyridin-2-yl)phosphine oxide. Magnetism and spin crossover in the (pz)3CH case
  作者：Peter A. Anderson、Timothy Astley、Michael A. Hitchman、F. Richard Keene、Boujemaa Moubaraki、Keith S. Murray、Brian W. Skelton、Edward R. T. Tiekink、Hans Toftlund、Allan H. White

  DOI：10.1039/b003299i

  日期：——

  range of six-co-ordinate bis-tripodal iron(II) chelates, [FeL2]2+, has been synthesized from iron-(II) or -(III) precursors where L = tris(pyrazol-1-yl)methane (pz)3CH, tris(pyridyl-2-yl)methane (py)3CH, bis(pyrazol-1-yl)(pyridin-2-yl)methane (pz)2(py)CH and tris(pyridin-2-yl)phosphine oxide (py)3PO. Crystal structures have been determined for three compounds and in the (pz)3CH case for two polymorphs

  从铁（II）或-（III）前体合成了一系列六坐标的双三脚铁（II）螯合物[FeL 2 ] 2+，其中L =三（吡唑-1-基）甲烷（PZ）3 CH，三（吡啶-2-基）甲烷（py）3 CH，双（吡唑-1-基）（吡啶-2-基）甲烷（PZ）2（py）CH和三（吡啶-2-基）氧化膦（PY）3 P O.晶体结构已被确定为三种化合物并且在（PZ）3 CH的情况下，其为分别在两个不同的实验室从铁（得到两种多晶型（α和β）III使用不同的）盐结晶化 溶剂。[FeL 2 ] 2+系列的电子性质已通过光谱学测量进行了研究。指示了低旋转d 6行为。在[Fe （PZ）3 CH} 2 ] 2+上的磁和莫斯鲍尔效应测量结果表明，在高于270 K时会发生自旋转变为高自旋态，尽管远未达到350K。博学多才的硼配体类似物[Fe （PZ）3 BH} 2 ]，具有相似的交叉行为，并且含有双（三齿）配体配合物配体 1,4,7-三氮杂环壬烷。
• N-Oxides of 1,1,1-Tris(pyrid-2-yl)ethane
  作者：Ahmed Nada、Mohammed Almansouri、Abdulrahman Al-Harbi、Jameel Al-Thagafi、Abdul Malik P. Peedikakkal、Ahmed Al-Harbi

  DOI：10.1016/j.tetlet.2020.152326

  日期：2020.9

  compounds, namely: 1,1,1-tris(pyrid-2-yl)ethane N-oxide, 1,1,1-tris(pyrid-2-yl)ethane N,N′-dioxide and 1,1,1-tris(pyrid-2-yl)ethane N,N′, N″-trioxide. The Mono-N-oxide is formed by treatment of the parent pyridine compound with hydrogen peroxide in acetic acid at 100 °C. On the other hand, treating the corresponding pyridine with m-chloroperbenzoic acid(m-CPBA) in chloroform at reflux led to a mixture of di

  在这里，我们报告了一种新型的吡啶-N-氧化物化合物的合成，即：1,1,1-三（吡啶-2-基）乙烷N-氧化物，1,1,1-三（吡啶-2-基） yl）乙烷N，N'-二氧化物和1,1,1-三（吡啶-2-基）乙烷N，N ' ，N '' -三氧化物。的单声道- ñ氧化物是通过处理与过氧化氢在乙酸中于100℃母体吡啶化合物的形成。另一方面，用氯仿中的间氯过苯甲酸（m-CPBA）在回流下处理相应的吡啶，得到二和三-N-氧化物的混合物。
• Interaction of palladium(<scp>II</scp>) with polydentate ligands, including the synthesis and structure of bis[tris(pyrazol-1-yl)borato-N,N′]palladium(<scp>II</scp>) and the cations [Pd(L)₂]²⁺[L = tris(pyrazol-1-yl)methane-N,N′ or tris(pyridin-2-yl)methane-N,N′]
  作者：Allan J. Canty、Nigel J. Minchin、Lutz M. Engelhardt、Brian W. Skelton、Allan H. White

  DOI：10.1039/dt9860000645

  日期：——

  benzene. X-Ray crystallographic studies show that for complexes (1)–(3) the potentially tridentate ligands are present as N,N′-bidentates to give square-planar PdN4 geometry with a crystallographic centre of symmetry at palladium(II). 1H N.m.r. spectra are consistent with similar structures in solution, with facile interconversion between co-ordinated and unco-ordinated ring environments. Complex (3) crystallises

  钯（II）形成络合物[Pd HB（pz）3 } 2 ]（1），[Pd （py）3 CH} 2 ] [NO 3 ] 2（3）和[Pd （pz）3 CH} 2 ] X 2 [X = NO 3 – BF 4 –（2）或ClO 4 – ]与四氯palladate（II）与三（吡唑-1-基）硼酸[HB（pz）3 ] – }，并从[Pd（L）C1 2中除去氯配体通过AgX ] L =三（吡啶-2-基）甲烷[（py）3 CH]或三（吡唑-1-基）甲烷[（pz）3 CH]}，然后再加一摩尔配体L氯配合物[Pd（L）Cl 2 ]由水溶液中的[PdCl 4 ] 2–和（py）3 CH以及水溶液中的[Pd（NCPh）2 Cl 2 ]和（pz）3 CH制备。苯。X射线晶体学研究表明，对于配合物（1）–（3），潜在的三齿配体以N，N′-双齿形式存在，从而得到方形PdN 4在钯（II）上具有对称的晶体学中心的几何形状。1
• Co-ordination chemistry of dimethylgold(III). Synthesis, spectroscopic, and structural studies of complexes with neutral aromatic nitrogen-donor ligands
  作者：Allan J. Canty、Nigel J. Minchin、Peter C. Healy、Allan H. White

  DOI：10.1039/dt9820001795

  日期：——

  cis-square-planar co-ordination for gold(III), AuC2N2, with Au–C 2.023(7)–2.041(12)Å and Au–N 2.127(8)–2.142(8)Å. In complexes of the potential tridentate ligands one pyridyl group is not co-ordinated in the tpm complex, and one pyrazolyl group is involved in a weak axial Au ⋯ N interaction [3.139(7)Å] in the tpzm complex. Comparison of the 1H n.m.r. spectra of complexes of the potentially tridentate ligands (tpzm

  硝酸二甲基金（III）与中性配体反应形成配合物[AuMe 2（tpm）] NO 3 ·2H 2 O（tpm =三-2-吡啶甲烷）和[AuMe 2 L] NO 3 [L = tri-2-吡啶甲醇（tpmo），二-2-吡啶基甲烷（dpm），αα-二-2-吡啶基甲苯（dpt），二-1-吡唑基甲烷（dpzm）和三-1-吡唑基甲烷（tpzm）]。已经通过在295 K下进行单晶X射线衍射确定了tpzm，tpm和dpt的配合物的晶体结构，并通过最小二乘法将3,043,1,616和3的R分别设为R = 0.033、0.029和0.042。分别有2 529个独立的“观察”反射。在这些结构中，[AuMe 2 L]+阳离子对于金（ III），AuC 2 N 2，Au–C 2.023（7）–2.041（12）Å和Au–N 2.127（8）–2.142（8）本质上具有顺式-方形平面配位作用一种。在潜在的三齿配体的配