tris(3-methyl-2-pyridylmethyl)-amine | 202192-54-9

• 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(3-methyl-2-pyridylmethyl)-amine
• 英文别名: tris(2-(6-methylpyridine)methyl)amine；tris(6-methyl-2-pyridylmethyl)amine；6-Me3-TPA；1-(3-methylpyridin-2-yl)-N,N-bis[(3-methylpyridin-2-yl)methyl]methanamine
• CAS: 202192-54-9
• 化学式: C₂₁H₂₄N₄
• 分子量: 332.448
• InChiKey: DOPDHQOGKHPYAP-UHFFFAOYSA-N

物化性质

• 沸点：
  464.4±40.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  41.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  iron perchlorate hexahydrate 、 tris(3-methyl-2-pyridylmethyl)-amine 在 三乙胺 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Raman Signature of the Fe₂O₂ “Diamond” Core

  摘要：

  We report the resonance Raman (RR) spectra of iron complexes containing the Fe-2(mu-O)(2) core. Frozen CH3CN solutions of the (FeFeIV)-Fe-III intermediate [Fe-2(mu-O)(2)L-2](ClO4)(3) (where L = TPA, 5-Me-3-TPA, 5-Me-2-TPA, 5-MeTPA, 5-Et-3-TPA, or 3-Me-3-TPA) show numerous resonance-enhanced vibrations, and among these, an oxygen-isotope-sensitive vibration around 667 cm(-1) that shifts ca. 30 cm(-1) when the samples are allowed to exchange with (OH2)-O-18, and whose Raman shift does not vary with methyl substitution of the TPA ligand. Spectra of iron-isotope-substituted samples of [Fe-2(mu-O)(2)(L)2(])(ClO4)(3) (Fe-54 and Fe-57 for L = TPA, and Fe-54 and Fe-58 for L = 5-Me-3-TPA) show that this vibration is also iron-isotope sensitive. These isotopic data taken together strongly suggest that this vibration involves motion of the Fe-2(mu-O)(2) core that is isolated from motions of the Ligand. A frozen CH3CN solution of the diiron(III) complex [Fe-2(mu-O)(2)(6-Me-3-TPA)(2)](ClO4)(2) shows one intense resonance-enhanced vibration at 692 cm(-1) that shifts -30 cm(-1) with O-18 labeling. Normal coordinate analysis of the Fe-2(mu-O)(2) core in [Fe-2(mu-O)(2)(5-Me-3-TPA)(2)](ClO4)(3) supports the assignment of the Fermi doublet centered around 666.2 cm(-1) as an A(1) vibration of this core. Furthermore, we propose that this unique feature found in the region between 650 and 700 cm(-1) is indicative of a diamond core structure and is the Raman signature of an iron cluster containing this core.

  DOI：

  10.1021/ja973220u
• 作为产物：
  描述：

  2-(氯甲基)-3-甲基吡啶盐酸盐 、 2-aminomethyl-3-methylpyridine hydrochloride 在 sodium hydroxide 作用下， 反应 48.0h， 以64%的产率得到tris(3-methyl-2-pyridylmethyl)-amine
  参考文献：
  名称：

  Raman Signature of the Fe₂O₂ “Diamond” Core

  摘要：

  We report the resonance Raman (RR) spectra of iron complexes containing the Fe-2(mu-O)(2) core. Frozen CH3CN solutions of the (FeFeIV)-Fe-III intermediate [Fe-2(mu-O)(2)L-2](ClO4)(3) (where L = TPA, 5-Me-3-TPA, 5-Me-2-TPA, 5-MeTPA, 5-Et-3-TPA, or 3-Me-3-TPA) show numerous resonance-enhanced vibrations, and among these, an oxygen-isotope-sensitive vibration around 667 cm(-1) that shifts ca. 30 cm(-1) when the samples are allowed to exchange with (OH2)-O-18, and whose Raman shift does not vary with methyl substitution of the TPA ligand. Spectra of iron-isotope-substituted samples of [Fe-2(mu-O)(2)(L)2(])(ClO4)(3) (Fe-54 and Fe-57 for L = TPA, and Fe-54 and Fe-58 for L = 5-Me-3-TPA) show that this vibration is also iron-isotope sensitive. These isotopic data taken together strongly suggest that this vibration involves motion of the Fe-2(mu-O)(2) core that is isolated from motions of the Ligand. A frozen CH3CN solution of the diiron(III) complex [Fe-2(mu-O)(2)(6-Me-3-TPA)(2)](ClO4)(2) shows one intense resonance-enhanced vibration at 692 cm(-1) that shifts -30 cm(-1) with O-18 labeling. Normal coordinate analysis of the Fe-2(mu-O)(2) core in [Fe-2(mu-O)(2)(5-Me-3-TPA)(2)](ClO4)(3) supports the assignment of the Fermi doublet centered around 666.2 cm(-1) as an A(1) vibration of this core. Furthermore, we propose that this unique feature found in the region between 650 and 700 cm(-1) is indicative of a diamond core structure and is the Raman signature of an iron cluster containing this core.

  DOI：

  10.1021/ja973220u

文献信息

• Stereospecific Alkane Hydroxylation by Non-Heme Iron Catalysts:  Mechanistic Evidence for an Fe^VO Active Species
  作者：Kui Chen、Lawrence Que

  DOI：10.1021/ja010310x

  日期：2001.7.1

  iron-oxo species have frequently been invoked in the oxidation of hydrocarbons by both heme and non-heme enzymes. Although a formally Fe(V)=O species, that is, [(Por(*))Fe(IV)=O](+), has been widely accepted as the key oxidant in stereospecific alkane hydroxylation by heme systems, it is not established that such a high-valent state can be accessed by a non-heme ligand environment. Herein we report a systematic

  血红素和非血红素酶在碳氢化合物的氧化中经常调用高价铁氧类物质。尽管形式上的 Fe(V)=O 物种，即 [(Por(*))Fe(IV)=O](+) 已被广泛接受为血红素系统立体有择烷烃羟基化的关键氧化剂，但它是尚未确定非血红素配体环境可以访问这种高价态。在此，我们报告了对由一组非血红素铁配合物催化的 H(2)O(2) 烷烃氧化的系统研究，即 [Fe(II)(TPA)(CH(3)CN)(2) ](2+) (1, TPA = tris(2-pyridylmethyl)amine) 及其α-和β-取代的类似物。该系列 Fe(II)(TPA) 催化剂的反应模式可以通过配体环境的电子和空间特性进行调节，这会影响常见的 Fe(III)-OOH 中间体的自旋态。当 TPA 配体具有两个或三个 α 取代基时，这种 Fe(III)-过氧物种是高自旋的，并且被提议直接负责烷烃底物的选择性 CH 键断裂。然而，由
• Synthesis and Spectroscopy of μ-Oxo (O²^-)-Bridged Heme/Non-heme Diiron Complexes:  Models for the Active Site of Nitric Oxide Reductase
  作者：Ian M. Wasser、Constantinus F. Martens、Claudio N. Verani、Eva Rentschler、Hong-wei Huang、Pierre Moënne-Loccoz、Lev N. Zakharov、Arnold L. Rheingold、Kenneth D. Karlin

  DOI：10.1021/ic0348143

  日期：2004.1.1

  6-difluorophenyl)porphine, is reported. The crystal structure for 1.PF(6) reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe' moiety; 90 degree angle (Fe-O-Fe') = 166.7(3) degrees, and d(Fe.Fe') = 3.556 A. Crystal data for C(70)H(57)ClF(12)Fe(2)N(8)O(3)P (1.PF(6)): triclinic, Ponemacr;, a = 13.185(3) A, b = 14.590 (3) A, c = 16.885(4) A, alpha = 104.219(4) degrees, beta = 91.572(4) degrees

  在本文中，我们描述了由卟啉和三脚架氮配体TMPA [TMPA = tris（2-pyridylmethyl）amine]支撑的一系列血红素/非血红素Fe-O-Fe'配合物的合成和研究。[[（（6）L）Fe-O-Fe（X）]（+）（1）的完整合成（X = OMe（-）或Cl（-），比例为69:31），其中（6）L是5-（oO-[（N，N-双（2-吡啶基甲基）-2-（6-甲氧基）吡啶甲基甲胺）苯基] -10,15,20-三（2,6-二氟苯基）卟啉的二价阴离子， 1.PF（6）的晶体结构揭示了一个分子内血红素/非血红素二铁络合物，由Fe-O-Fe'部分桥接； 90度角（Fe-O-Fe'）= 166.7（3）度，d（Fe.Fe'）= 3.556 A.C（70）H（57）ClF（12）Fe（2）N（8）O（3）P（1.PF（6））的晶体数据：三斜晶，Ponemacr；，a ＝ 13.185（3）A，b
• Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes
  作者：Gemma K. Gransbury、Brooke N. Livesay、Jett T. Janetzki、Moya A. Hay、Robert W. Gable、Matthew P. Shores、Alyona Starikova、Colette Boskovic

  DOI：10.1021/jacs.0c01073

  日期：2020.6.17

  Bis(dioxolene)-bridged dinuclear cobalt compounds provide an avenue toward controlled two-step valence tautomeric (VT) interconversions of the form CoIII-cat-cat-CoIII} ⇌ CoIII-cat-SQ-CoII} ⇌ CoII-SQ-SQ-CoII} (cat2- = catecholate, SQ•- = semiquinonate). The four dinuclear cobalt complexes in this study are bridged by deprotonated 3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-5,5',6,6'-tetraol (spiroH4)

  双(二氧戊环)-桥连双核钴化合物为 CoIII-cat-cat-CoIII} ⇌ CoIII-cat-SQ-CoII} ⇌ CoII-SQ 形式的受控两步价互变异构 (VT) 互变提供了途径-SQ-CoII}（cat2- = 儿茶酚酸盐，SQ•- = 半醌酸盐）。本研究中的四种双核钴配合物由去质子化的 3,3,3',3'-四甲基-1,1'-螺二（茚满）-5,5',6,6'-四醇（spiroH4）或 3 ,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4',7,7'-tetrabromo-5,5',6,6'-tetraol (Br4spiroH4) 与 Mentpa 辅助配体（tpa = 三（2-吡啶基甲基）胺，n = 0-3 对应于吡啶环 6 位的甲基化）。互补的结构、磁性、光谱和 DFT 计算研究揭示了四种钴配合物的不同电子结构和 VT 行为；
• Resonance Raman Studies of the Iron(II)−α-Keto Acid Chromophore in Model and Enzyme Complexes
  作者：Raymond Y. N. Ho、Mark P. Mehn、Eric L. Hegg、Aimin Liu、Matthew J. Ryle、Robert P. Hausinger、Lawrence Que

  DOI：10.1021/ja0041775

  日期：2001.5.1

  The bidentate coordination of an α-keto acid to an iron(II) center via the keto group and the carboxylate gives rise to metal-to-ligand charge-transfer transitions between 400 and 600 nm in model c...

  α-酮酸通过酮基和羧酸盐与铁 (II) 中心的双齿配位在模型 c 中产生 400 到 600 nm 之间的金属到配体的电荷转移跃迁。
• Chiral induction upon coordination to form an enantiomeric bis-chelate ruthenium(II)–tris(3-methyl-2-pyridylmethyl)amine complex
  作者：Takahiko Kojima、Yoshihisa Matsuda

  DOI：10.1039/b100095k

  日期：——

  Chiral induction to a C3-symmetric and non-prochiral tris(3-methyl-2-pyridylmethyl)amine was achieved upon coordination to a ruthenium(II) center by forming a stable fac–cis bis-chelate complex selectively and 1H NMR spectroscopy showed that the chirality is maintained even in solution.

  通过选择性地形成稳定的面顺式双螯合物配合物和 1H NMR 光谱，在与钌 (II) 中心配位后，实现了对 C3 对称和非前手性三（3-甲基-2-吡啶基甲基）胺的手性诱导表明即使在溶液中也能保持手性。