4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine | 1392139-13-7

• 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: 4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine
• 英文别名: 4,6-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-2-phenylpyrimidine；N-[[6-[[bis(pyridin-2-ylmethyl)amino]methyl]-2-phenylpyrimidin-4-yl]methyl]-1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine
• CAS: 1392139-13-7
• 化学式: C₃₆H₃₄N₈
• 分子量: 578.72
• InChiKey: QMKSQYXLKCKJLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  83.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [Fe^II(pyridine)₄(NCSe)₂] 、 4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine 以 甲醇 为溶剂， 反应 1.17h， 以82%的产率得到
  参考文献：
  名称：

  Nine Diiron(II) Complexes of Three Bis-tetradentate Pyrimidine Based Ligands with NCE (E = S, Se, BH₃) Coligands

  摘要：

  Three bis-tetradentate acyclic amine ligands differing only in the arm length of the pyridine pendant arms attached to the 4,6-positions of the pyrimidine ring, namely, 4,6-bis[N,N-bis(2'-pyridylethyl)aminomethyl]-2-phenylpyrimidine (L-Et), 4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine (L-Me), and 4,6-[(2'-pyridylmethyl)-2'-pyridylethyl)aminomethyl]-2-phenylpyrimidine (L-Mix) have been used to synthesize nine air-sensitive diiron(II) complexes: [(Fe2LEt)-L-II(NCS)(4)]center dot MeOH center dot 3/4H(2)O (1 center dot MeOH center dot 3/4H(2)O), [(Fe2LEt)-L-II(NCSe)(4)]center dot H2O (2 center dot H2O), [(Fe2LEt)-L-II(NCBH3)(4)]center dot 5/2H(2)O (3 center dot 5/2H(2)O), [(Fe2LEt)-L-II(NCS)(4)]center dot 1/2H(2)O (4 center dot 1/2H(2)O), [(Fe2LEt)-L-II(NCSe)(4)] (5), [(Fe2LEt)-L-II(NCBH3)(4)]center dot 3/2H(2)O (6 center dot 3/2H(2)O), [(Fe2LMix)-L-II(NCS)(4)]center dot 1/2H(2)O (7 center dot 1/2H(2)O), [(Fe2LMix)-L-II(NCSe)(4)]center dot 3/2H(2)O (8 center dot 3/2H(2)O), and [(Fe2LMix)-L-II(NCBH3)(4)]center dot 3/2H(2)O (9 center dot 3/2H(2)O). Complexes 3 center dot 5/2H(2)O, 4 center dot 1/2H(2)O, 5, 6 center dot 3/2H(2)O, and 8 center dot 3/2H(2)O were structurally characterized by X-ray crystallography, revealing, in all cases, both of the iron(II) centers in an octahedral environment with two NCE (E = S, Se, or BH3) anions in a cis-position relative to one another. Variable temperature magnetic susceptibility measurements showed that: all nine diiron(II) complexes are stabilized in the [HS-HS] state from 300 K to 4 K, and exhibit weak antiferromagnetic coupling. Mossbauer spectroscopy confirmed the spin and oxidation states of eight of the nine complexes (the synthesis of air-sensitive complex 3 was not readily reproduced).

  DOI：

  10.1021/ic3012052
• 作为产物：
  描述：

  4,6-bis(hydroxymethyl)-2-phenylpyrimidine 在 氯化亚砜 、 sodium carbonate 、 potassium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine
  参考文献：
  名称：

  Nine Diiron(II) Complexes of Three Bis-tetradentate Pyrimidine Based Ligands with NCE (E = S, Se, BH₃) Coligands

  摘要：

  Three bis-tetradentate acyclic amine ligands differing only in the arm length of the pyridine pendant arms attached to the 4,6-positions of the pyrimidine ring, namely, 4,6-bis[N,N-bis(2'-pyridylethyl)aminomethyl]-2-phenylpyrimidine (L-Et), 4,6-bis[N,N-bis(2'-pyridylmethyl)aminomethyl]-2-phenylpyrimidine (L-Me), and 4,6-[(2'-pyridylmethyl)-2'-pyridylethyl)aminomethyl]-2-phenylpyrimidine (L-Mix) have been used to synthesize nine air-sensitive diiron(II) complexes: [(Fe2LEt)-L-II(NCS)(4)]center dot MeOH center dot 3/4H(2)O (1 center dot MeOH center dot 3/4H(2)O), [(Fe2LEt)-L-II(NCSe)(4)]center dot H2O (2 center dot H2O), [(Fe2LEt)-L-II(NCBH3)(4)]center dot 5/2H(2)O (3 center dot 5/2H(2)O), [(Fe2LEt)-L-II(NCS)(4)]center dot 1/2H(2)O (4 center dot 1/2H(2)O), [(Fe2LEt)-L-II(NCSe)(4)] (5), [(Fe2LEt)-L-II(NCBH3)(4)]center dot 3/2H(2)O (6 center dot 3/2H(2)O), [(Fe2LMix)-L-II(NCS)(4)]center dot 1/2H(2)O (7 center dot 1/2H(2)O), [(Fe2LMix)-L-II(NCSe)(4)]center dot 3/2H(2)O (8 center dot 3/2H(2)O), and [(Fe2LMix)-L-II(NCBH3)(4)]center dot 3/2H(2)O (9 center dot 3/2H(2)O). Complexes 3 center dot 5/2H(2)O, 4 center dot 1/2H(2)O, 5, 6 center dot 3/2H(2)O, and 8 center dot 3/2H(2)O were structurally characterized by X-ray crystallography, revealing, in all cases, both of the iron(II) centers in an octahedral environment with two NCE (E = S, Se, or BH3) anions in a cis-position relative to one another. Variable temperature magnetic susceptibility measurements showed that: all nine diiron(II) complexes are stabilized in the [HS-HS] state from 300 K to 4 K, and exhibit weak antiferromagnetic coupling. Mossbauer spectroscopy confirmed the spin and oxidation states of eight of the nine complexes (the synthesis of air-sensitive complex 3 was not readily reproduced).

  DOI：

  10.1021/ic3012052

文献信息

• Di‐ and Tetranuclear Complexes of Bis‐Tetradentate Pyrimidine‐Based Ligands with All‐Methylene‐ Versus Mixed Methylene/Ethylene‐Linked Arms
  作者：Worku A. Gobeze、Victoria A. Milway、Nicholas F. Chilton、Boujemaa Moubaraki、Keith S. Murray、Sally Brooker

  DOI：10.1002/ejic.201300368

  日期：2013.9.2

  [NiII4(LMe)2F4](BF4)4 (16) and NiII4(LMix)2F4(BF4)4??8H2O (17). Dinuclear complexes were obtained from the reactions conducted in MeCN, whereas tetranuclear complexes resulted from reactions performed in MeOH. Five dimetallic (3??????6??? and 9???) and one tetrametallic complex (15???) were structurally characterized: the ligands are bis-tetradentate and the metal centres are bridged through the pyrimidine

  [NiII4(LMe)2F4](BF4)4 (16) 和 NiII4(LMix)2F4( )4??8H2O (17)。双核配合物由在 MeCN 中进行的反应获得，而四核配合物由在 MeOH 中进行的反应产生。五个双金属（3??????6???和9???）和一个四金属配合物（15???）的结构特征：配体是双四齿的，金属中心通过嘧啶环桥接. 在四金属 15 ??? 中，两个这样的双金属片段由两对氟阴离子桥接。在所有情况下，双核 1?8 和四核 13?15 的变温磁化率测量和海森堡拟合揭示了高自旋金属中心之间的弱分子内反铁磁交换耦合。还对二钴 (II) 配合物 4 进行了严格的自旋轨道和交换分析。
• Two distinct tetranuclear motifs, rectangular vs. extended, are observed for complexes of a bis-tetradentate pyrimidine-based ligand
  作者：Worku A. Gobeze、Sally Brooker

  DOI：10.1039/c3ra45091k

  日期：——

  The 1 : 2 reactions of 4,6-bis[N,N-bis(2′-pyridylmethyl)aminomethyl]-2-phenylpyrimidine (LMe) and MnII, CoII, NiII and CuII chloride salts in MeOH gave the tetranuclear complexes [MnII4(LMe)2Cl8]·2H2O (1), CoII4(LMe)2Cl8·10H2O (2), [Ni4II(LMe)2Cl4]Cl4·8H2O (3) and [CuII4(LMe)2Cl6]Cl2·8H2O (4), respectively. X-ray crystal structure determinations carried out on three of the complexes revealed that in the case of NiII (3′) the LMe ligand is bound in the expected bis-tetradentate fashion, bridging the encapsulated pair of NiII centers via the pyrimidine ring, and that two pairs of chloride anions bridge a pair of such dimetallic units, affording a closed rectangular tetranuclear core overall. In contrast, in the case of MnII (1′) and CuII (4′) only one binding pocket of the LMe ligand strand binds in the expected tetradentate manner, whilst the other binds in a terdentate manner as one pyrimidine nitrogen atom does not bind, so in these cases the pyrimidine moiety does not bridge the metal centres, resulting instead in ‘extended’, linear tetranuclear assemblies.

  1 ： 4,6-双[N,N-双(2′-吡啶基甲基)氨基甲基]-2-苯基嘧啶(LMe)与 MnII、CoII、NiII 和 CuII 氯盐在 MeOH 中发生 1 : 2 反应，生成四核配合物 [MnII4(LMe)2Cl8]-2H2O (1)、CoII4(LMe)2Cl8-10H2O (2)、[Ni4II(LMe)2Cl4]Cl4-8H2O (3) 和 [CuII4(LMe)2Cl6]Cl2-8H2O (4)。对其中三个复合物进行的 X 射线晶体结构测定显示，在 NiII (3′) 复合物中，LMe 配体以预期的双-四价方式结合，通过嘧啶环桥接封装的一对 NiII 中心，两对氯阴离子桥接一对这样的二金属单元，形成一个封闭的矩形四核核心。相反，在 MnII（1′）和 CuII（4′）的情况中，只有 LMe 配体链的一个结合袋以预期的四价方式结合，而另一个结合袋则以三价方式结合，因为一个嘧啶氮原子没有结合，所以在这些情况中，嘧啶分子没有桥接金属中心，而是形成了 "扩展 "的线性四核集合体。