Fe3(OAc)6(1,1-bis(1-methyl-2-imidazolyl)-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane)2 | 162614-48-4

• 英文名称: Fe3(OAc)6(1,1-bis(1-methyl-2-imidazolyl)-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane)2
• CAS: 162614-48-4
• 化学式: C₆₀H₈₆Fe₃N₈O₁₄
• 分子量: 1310.93
• InChiKey: PPZRRLYOPMJXTN-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  iron(II) acetate 、 1,1-bis(2-(1-methylimidazolyl))-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane 以 甲醇 为溶剂， 以79%的产率得到Fe3(OAc)6(1,1-bis(1-methyl-2-imidazolyl)-1-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane)2
  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