2,2'-bis(1-methylimidazolyl)phenylhydroxymethane | 131154-61-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2,2'-bis(1-methylimidazolyl)phenylhydroxymethane
• 英文别名: bis(1-methyl-2-imidazolyl)phenylhydroxymethane；Bis(1-methylimidazol-2-yl)-phenylmethanol
• CAS: 131154-61-5
• 化学式: C₁₅H₁₆N₄O
• 分子量: 268.318
• InChiKey: NWIYARUDRHTEHU-UHFFFAOYSA-N

物化性质

• 沸点：
  550.1±50.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)
• 溶解度：
  >40.2 [ug/mL]

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  55.9
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  iron(II) acetate 、 2,2'-bis(1-methylimidazolyl)phenylhydroxymethane 以 甲醇 为溶剂， 以41%的产率得到Fe3(OAc)6(bis(1-methyl-2-imidazolyl)phenylhydroxymethane)2 * 2 MeOH
  参考文献：
  名称：

  Ferromagnetic versus Antiferromagnetic Exchange in Five Structurally Analogous Carboxylate-Bridged Trinuclear Ferrous Complexes

  摘要：

  The synthesis, structural characterization, and magnetic properties of linear, trinuclear complexes of general formula [Fe-3(O(2)CR)(6)L(2)] are reported. Addition of Fe(OAc)(2) to the bidentate nitrogen donor ligands bis(1-methyl-2-imidazolyl)phenylhydroxymethane (BIPhOH) and 1,1-bis(1-methyl-2-imidazolyl)-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane (BIDPhEH) afforded [Fe-3(OAc)(6)(BIPhOH)(2)]. 2MeOH (3) and [Fe-3(OAc)(6)(BIDPhEH)(2)] (4), respectively. Complex 3 crystallizes in P ($) over bar 1, with a = 8.985(2) Angstrom, b = 9.148(1) Angstrom, c = 15.761(2) Angstrom, alpha = 80.73(1)degrees, beta = 81.28(1)degrees, gamma = 101.91(1)degrees, V = 1228.0(4) Angstrom(3), and Z = 1 (R = 0.046, R(W) 0.056), and complex 4 crystallizes in P2(1)/n, with a = 12.809(5) Angstrom, b = 22.214(5) Angstrom, c = 13.793(5) Angstrom, beta = 91.19(2)degrees, V = 3924(2) Angstrom(3), and Z = 2 (R = 0.055, R(W) = 0.076). Addition of Fe(BF4)(2) . 6H(2)O and sodium benzoate to the ligands bis[2-((4S)-(1-methylethyl)-1,3-oxazolinyl)]methane ((i)PrOx) and N,N,N'-trimethyl-N'-[4,4-dimethyl-4-(3,5-di-tert-butyl-4-hydroxyphenyl)butyl]ethylenediamine (PheMe(3)Eda) yielded compounds [Fe-3(O(2)CPh)(6)((i)PrOx)(2)] (5) and [Fe-3(O(2)CPh)(6)(PheMe(3)Eda)(2)] (6), respectively. Compound 5 crystallizes in P2(1)2(1)2(1), with a = 14.677(3) Angstrom, b = 19.289(4) Angstrom, c = 23.066(6) Angstrom, V = 6530(4) Angstrom(3), and Z = 4 (R = 0.059, R(w) = 0.065), and compound 6 in P2(1)/n, with a = 10.111(1) Angstrom, b = 31.389(2) Angstrom, c = 14.243(2) Angstrom, beta = 100.76(5)degrees, V = 4441(1) Angstrom(3), and Z = 2 (R = 0.047, R(W) = 0.063). In all of these complexes, the iron atoms are linked by two bidentate and one unidentate bridging carboxylate ligands. The coordination spheres of the terminal iron atoms are completed by the bidentate nitrogen ligands and, in compounds 5 and 6, by the second ''dangling'' oxygen atom of the unidentate bridging carboxylate. We investigated the magnetic properties of these four compounds, as well as those of [Fe-3(OAc)(6)-(BIPhMe)(2)] (1), reported previously (Rardin, R. L.; Poganiuch, P.; Bino A.; Goldberg, D. P.; Tolman, W. B.; Liu, S.; Lippard, S. J. J. Am. Chem. Sec. 1992, 114, 5240-5249). Three of the complexes (1, 3, and 4) exhibit intramolecular ferromagnetic exchange coupling, J = -2 to -5 cm(-1) (H = JS(1) . S-2), resulting in high-spin S = 6 ground states, and the remaining two complexes are antiferromagnetically coupled, with S = 2 ground states. The magnetic properties thus correlate with the structural differences between the two classes of compounds. Both temperature-dependent magnetic susceptibility and high-field magnetization measurements reveal this behavior. The magnetic data were fit to a theoretical model incorporating exchange coupling, single-ion zero-field splitting, and g tenser anisotropy. A set of consensus magnetic parameters for each compound was obtained, with weak magnetic exchange (/J/ less than or equal to 5 cm(-1)) between nearest-neighbor iron atoms being a common feature for all five compounds. The X-band EPR spectra of 1, 3, and 4 at 4 K displayed broad, low-field (g(obs) approximate to 18) signals consistent with integer-spin ground states.These spectra an remarkably similar to those of the reduced, diiron(II) centers found in the non-heme iron proteins methane monooxygenase (MMOH), hemerythrin (Hr), and the R2 protein of ribonucleotide reductase. Theoretical calculations indicate that several allowed EPR transitions from the resulting manifold of ground and low-lying excited energy levels arising from the integer spin (S = 6) state could be responsible for the broad low-field absorption feature.

  DOI：

  10.1021/ic00115a032
• 作为产物：
  描述：

  N-甲基咪唑 、 苯甲酰氯 在 正丁基锂 作用下， 生成 2,2'-bis(1-methylimidazolyl)phenylhydroxymethane
  参考文献：
  名称：

  聚铁氧蛋白的还原形式模型：不对称的三羧酸桥连二铁（II）复合物及其与双氧的反应

  摘要：

  一种二铁 (II) 模型化合物已制备并通过元素分析表征，其特征与多铁-氧代蛋白 hemerythrin (Hr)、核糖核苷酸还原酶 (RR) 和甲烷单加氧酶 (MMO) 的还原形式的活性位点相关， X 射线晶体学、磁化率测量和 Mossbauer、UV-vis、IR、1 H NMR 和 RPT 光谱

  DOI：

  10.1021/ja00001a023

文献信息

• Ferromagnetic versus Antiferromagnetic Exchange in Five Structurally Analogous Carboxylate-Bridged Trinuclear Ferrous Complexes
  作者：David P. Goldberg、Joshua Telser、Cecilia M. Bastos、Stephen J. Lippard

  DOI：10.1021/ic00115a032

  日期：1995.5

  The synthesis, structural characterization, and magnetic properties of linear, trinuclear complexes of general formula [Fe-3(O(2)CR)(6)L(2)] are reported. Addition of Fe(OAc)(2) to the bidentate nitrogen donor ligands bis(1-methyl-2-imidazolyl)phenylhydroxymethane (BIPhOH) and 1,1-bis(1-methyl-2-imidazolyl)-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane (BIDPhEH) afforded [Fe-3(OAc)(6)(BIPhOH)(2)]. 2MeOH (3) and [Fe-3(OAc)(6)(BIDPhEH)(2)] (4), respectively. Complex 3 crystallizes in P ($) over bar 1, with a = 8.985(2) Angstrom, b = 9.148(1) Angstrom, c = 15.761(2) Angstrom, alpha = 80.73(1)degrees, beta = 81.28(1)degrees, gamma = 101.91(1)degrees, V = 1228.0(4) Angstrom(3), and Z = 1 (R = 0.046, R(W) 0.056), and complex 4 crystallizes in P2(1)/n, with a = 12.809(5) Angstrom, b = 22.214(5) Angstrom, c = 13.793(5) Angstrom, beta = 91.19(2)degrees, V = 3924(2) Angstrom(3), and Z = 2 (R = 0.055, R(W) = 0.076). Addition of Fe(BF4)(2) . 6H(2)O and sodium benzoate to the ligands bis[2-((4S)-(1-methylethyl)-1,3-oxazolinyl)]methane ((i)PrOx) and N,N,N'-trimethyl-N'-[4,4-dimethyl-4-(3,5-di-tert-butyl-4-hydroxyphenyl)butyl]ethylenediamine (PheMe(3)Eda) yielded compounds [Fe-3(O(2)CPh)(6)((i)PrOx)(2)] (5) and [Fe-3(O(2)CPh)(6)(PheMe(3)Eda)(2)] (6), respectively. Compound 5 crystallizes in P2(1)2(1)2(1), with a = 14.677(3) Angstrom, b = 19.289(4) Angstrom, c = 23.066(6) Angstrom, V = 6530(4) Angstrom(3), and Z = 4 (R = 0.059, R(w) = 0.065), and compound 6 in P2(1)/n, with a = 10.111(1) Angstrom, b = 31.389(2) Angstrom, c = 14.243(2) Angstrom, beta = 100.76(5)degrees, V = 4441(1) Angstrom(3), and Z = 2 (R = 0.047, R(W) = 0.063). In all of these complexes, the iron atoms are linked by two bidentate and one unidentate bridging carboxylate ligands. The coordination spheres of the terminal iron atoms are completed by the bidentate nitrogen ligands and, in compounds 5 and 6, by the second ''dangling'' oxygen atom of the unidentate bridging carboxylate. We investigated the magnetic properties of these four compounds, as well as those of [Fe-3(OAc)(6)-(BIPhMe)(2)] (1), reported previously (Rardin, R. L.; Poganiuch, P.; Bino A.; Goldberg, D. P.; Tolman, W. B.; Liu, S.; Lippard, S. J. J. Am. Chem. Sec. 1992, 114, 5240-5249). Three of the complexes (1, 3, and 4) exhibit intramolecular ferromagnetic exchange coupling, J = -2 to -5 cm(-1) (H = JS(1) . S-2), resulting in high-spin S = 6 ground states, and the remaining two complexes are antiferromagnetically coupled, with S = 2 ground states. The magnetic properties thus correlate with the structural differences between the two classes of compounds. Both temperature-dependent magnetic susceptibility and high-field magnetization measurements reveal this behavior. The magnetic data were fit to a theoretical model incorporating exchange coupling, single-ion zero-field splitting, and g tenser anisotropy. A set of consensus magnetic parameters for each compound was obtained, with weak magnetic exchange (/J/ less than or equal to 5 cm(-1)) between nearest-neighbor iron atoms being a common feature for all five compounds. The X-band EPR spectra of 1, 3, and 4 at 4 K displayed broad, low-field (g(obs) approximate to 18) signals consistent with integer-spin ground states.These spectra an remarkably similar to those of the reduced, diiron(II) centers found in the non-heme iron proteins methane monooxygenase (MMOH), hemerythrin (Hr), and the R2 protein of ribonucleotide reductase. Theoretical calculations indicate that several allowed EPR transitions from the resulting manifold of ground and low-lying excited energy levels arising from the integer spin (S = 6) state could be responsible for the broad low-field absorption feature.
• Models of the reduced forms of polyiron-oxo proteins: an asymmetric, triply carboxylate bridged diiron(II) complex and its reaction with dioxygen
  作者：William B. Tolman、Shuncheng Liu、James G. Bentsen、Stephen J. Lippard

  DOI：10.1021/ja00001a023

  日期：1991.1

  A diiron(II) model compound having features relevant to the active sites of the reduced forms of the polyiron-oxo proteins hemerythrin (Hr), ribonucleotide reductase (RR), and methane monooxygenase (MMO) has been prepared and characterized by elemental analysis, X-ray crystallography, magnetic susceptibility measurements, and Mossbauer, UV-vis, IR, 1 H NMR, and RPT spectroscopy

  一种二铁 (II) 模型化合物已制备并通过元素分析表征，其特征与多铁-氧代蛋白 hemerythrin (Hr)、核糖核苷酸还原酶 (RR) 和甲烷单加氧酶 (MMO) 的还原形式的活性位点相关， X 射线晶体学、磁化率测量和 Mossbauer、UV-vis、IR、1 H NMR 和 RPT 光谱