[(1,4,7-trimethyl-1,4,7-triazacyclononane)2Fe2(μ-Cl)3]BPh4 | 190205-10-8

• 英文名称: [(1,4,7-trimethyl-1,4,7-triazacyclononane)2Fe2(μ-Cl)3]BPh4
• 英文别名: [(N,N',N''-trimethyl-1,4,7-triazacyclononane)3Fe2Cl3][BPh4]
• CAS: 190205-10-8
• 化学式: C₁₈H₄₂Cl₃Fe₂N₆*C₂₄H₂₀B
• 分子量: 879.858
• InChiKey: KEDLEOHCOGNWPZ-UHFFFAOYSA-K

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：

  [{(1,4,7-trimethyl-1,4,7-triazacyclononane)Fe}2(μ-Cl)3][(1,4,7-trimethyl-1,4,7-triazacyclononane)FeCl3] 、 四苯硼钠 以 乙腈 为溶剂， 以77%的产率得到[(1,4,7-trimethyl-1,4,7-triazacyclononane)2Fe2(μ-Cl)3]BPh4
  参考文献：
  名称：

  Binding of π-Acceptor Ligands to (Triamine)iron(II) Complexes

  摘要：

  A series of (Me(3)TACN)Fe-II derivatives with soft coligands have been investigated, where Me(3)TACN is N,N',N "-trimethyl-1,3,7-triazacyclononane. Treatment of Me(3)TACN with FeCl2 afforded a compound with the empirical formula (Me(3)TACN)FeCl2 (1). Compound 1, which is a versatile precursor reagent, was shown by single-crystal X-ray diffraction to be the salt [(Me(3)TACN)(2)Fe2Cl3][(Me(3)TACN)FeCl3], containing isolated [(Me(3)TACN)(2)Fe2Cl3](+) and [(Me(3)TACN)FeCl3](-) subunits. Treatment of 1 with NaBPh4 gave the known [(Me(3)TACN)(2)Fe2Cl3]BPh4, while the addition of Me(3)TACN to FeCl42- gave [(Me(3)TACN)FeCl3](-). Oxygenation of 1 afforded [(Me(3)TACN)FeCl2](2)(mu-O), which was shown crystallographically to be centrosymmetric with a pair of distorted octahedral Fe centers. The Fe-N bond trans to the Fe-O bond is elongated by 0.2 A relative to the other Fe-N distances. Solutions of 1 and thiolates absorb CO to give [(Me(3)TACN)Fe(SPh)(CO)(2)]BPh4 and (Me(3)TACN)Fe(S2C2H4)(CO) (v(CO) = 1896 cm(-1)). Treatment of 1 with excess CN- afforded [(Me(3)TACN)Fe(CN)(3)](-), isolated as its PPh4+ salt 5. Crystallographic and spectroscopic studies show that 5 is low spin with a C-3 nu structure; its Fe-N distances contracted by 0.23 Angstrom relative to those in [(Me(3)TACN)FeCl3](-). Aqueous solutions of 1 bind CO upon the addition of CN- to produce (Me(3)TACN)Fe(CN)(2)(CO) (6). Analogous to 6 is (Me(3)TACN)Fe(CN)(2)(CNMe), prepared by methylation of 5. The metastable dicarbonyl [(Me(3)TACN)FeI(CO)(2)]I was prepared by treatment of FeI2(CO)(4) with Me3TACN and was crystallographically characterized as its BPh4- salt. Values of E-1/2 for [(Me(3)TACN)FeCl3](-), 5, and 6 are -0.409, -0.640, and 0.533 V vs Fc/Fc(+), respectively.

  DOI：

  10.1021/ic9912629

文献信息

• Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM^II(μ-X)₃M^IIL]BPh₄ (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane)
  作者：Ursula Bossek、Daniela Nühlen、Eckhard Bill、Thorsten Glaser、Carsten Krebs、Thomas Weyhermüller、Karl Wieghardt、Marek Lengen、A. X. Trautwein

  DOI：10.1021/ic970119h

  日期：1997.6.1

  The reaction of the divalent metal halides ZnCl2, ZnBr2, MnCl2 . 4CH(3)CN, MnBr2, FeCl2 . 4CH(3)CN, CoCl2 . 4CH(3)-CN, CoBr2, NiCl2 . 6H(2)O, and NiBr2, respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon addition of NaBPh4 the isomorphous series of complexes [LMII(u-X)(3)(ML)-L-II]BPh4: 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl; 6, Co, Cl; 7, Co, Br; 5, Ni, Cl; 9, Ni, Br, Six of these complexes have been structurally characterized by single-crystal X-ray crystallography; they crystallize in the triclinic space group (No. 2) with Z = 4. Crystal data areas follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) Angstrom, alpha = 97.30(1), beta = 93.58(1), gamma = 117.46(1)degrees; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) Angstrom, alpha = 97.16(3), beta = 93.37(3), gamma = 117.24(3)degrees; 5, a 16.658(3), b = 17.064(3), c = 17.741(4) Angstrom, alpha = 97.32(3), beta = 93.47(3), gamma = 117.36(3)degrees; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) Angstrom, alpha = 97.39(3), beta = 93.58(3), gamma = 117.39(3)degrees; 8, a = 16.608(3), b = 16.995(3), c = 17.555(3) Angstrom, alpha = 97.36(1), beta = 93.52(1), gamma = 117.52(1)degrees; 9, a 16.680(3), b = 17.016(2), c = 17.715(3)Angstrom, alpha = 96.99(1), beta = 93.70(1), gamma = 117.42(1)degrees. All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three mu(2)-Cl or mu(2)-Br bridging Ligands and two LM fragments and well-separated tetraphenylborate actions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (lambda lambda lambda) (or (delta delta delta)) conformation at both LM fragments and a meso form with an (lambda lambda lambda) conformation at one LM fragment and (delta delta delta) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d(5)d(5) high spin), 4 (d(5)d(5)), 6 (d(7)d(7) high spin), 7 (d(7)d(7)), 8 (d(8)d(8)), and 9 (d(8)d(8)) are intramolecularly, weakly antiferromagnetically coupled in each case. Surprisingly, the spins order ferromagnetically in 5 (d(6)d(6) high spin). This is in contrast to the previously reported complex [(thf)(3)-Fe-II(mu-Cl)(3)Fe-II(thf)(3)][SnCl5(thf)] (thf = tetrahydrofuran)(5) for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent Mossbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.