([phenyltris((tert-butylthio)methyl)borate]FeCl)2 | 1013928-00-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ([phenyltris((tert-butylthio)methyl)borate]FeCl)2
• 英文别名: ([PhTt(tBu)]FeCl)2；iron(2+);tris(tert-butylsulfanylmethyl)-phenylboranuide;dichloride
• CAS: 1013928-00-1
• 化学式: C₄₂H₇₆B₂Cl₂Fe₂S₆
• 分子量: 977.683
• InChiKey: FYBHTBVNWOVBRQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.11
• 重原子数：
  54
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  ([phenyltris((tert-butylthio)methyl)borate]FeCl)2 在 KC₈ 作用下， 以 not given 为溶剂， 生成 [κ2-phenyltris((tert-butylthio)methyl)borate]Fe(III)(1-adamantylimido) 、 [κ2-phenyltris((tert-butylthio)methyl)borate]Fe(diadamantyltetrazadiene)
  参考文献：
  名称：

  Monovalent Iron in a Sulfur-Rich Environment

  摘要：

  A series of low-coordinate, paramagnetic iron complexes in a tris(thioether) ligand environment have been prepared. Reduction of ferrous {[PhTt(tBu)]FeCl}(2) [1; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate] with KC8 in the presence of PR3 (R = Me or Et) yields the high-spin, monovalent iron phosphine complexes [PhTt(tBu)]Fe(PR3) (2). These complexes provide entry into other low-valent derivatives via ligand substitution. Carbonylation led to smooth formation of the low-spin dicarbonyl [PhTttBu]Fe(CO)2 (3). Alternatively, replacement of PR3 with diphenylacetylene produced the high-spin alkyne complex [PhTt(tBu)]Fe(PhCCPh) (4). Lastly, 2 equiv of adamantyl azide undergoes a 3 + 2 cycloaddition at 2, yielding high-spin dialkyltetraazadiene complex 5.

  DOI：

  10.1021/ic7023378
• 作为产物：
  描述：

  iron(dichloride)*1.5(tetrahydrofuran) 、 tallium phenyltris((tert-butylthio)methyl)borate 以 四氢呋喃 为溶剂， 生成 ([phenyltris((tert-butylthio)methyl)borate]FeCl)2
  参考文献：
  名称：

  Monovalent Iron in a Sulfur-Rich Environment

  摘要：

  A series of low-coordinate, paramagnetic iron complexes in a tris(thioether) ligand environment have been prepared. Reduction of ferrous {[PhTt(tBu)]FeCl}(2) [1; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate] with KC8 in the presence of PR3 (R = Me or Et) yields the high-spin, monovalent iron phosphine complexes [PhTt(tBu)]Fe(PR3) (2). These complexes provide entry into other low-valent derivatives via ligand substitution. Carbonylation led to smooth formation of the low-spin dicarbonyl [PhTttBu]Fe(CO)2 (3). Alternatively, replacement of PR3 with diphenylacetylene produced the high-spin alkyne complex [PhTt(tBu)]Fe(PhCCPh) (4). Lastly, 2 equiv of adamantyl azide undergoes a 3 + 2 cycloaddition at 2, yielding high-spin dialkyltetraazadiene complex 5.

  DOI：

  10.1021/ic7023378

文献信息

• A High-Spin Organometallic Fe−S Compound: Structural and Mössbauer Spectroscopic Studies of [Phenyltris((<i>tert</i>-butylthio)methyl)borate]Fe(Me)
  作者：Codrina V. Popescu、Michael T. Mock、Sebastian A. Stoian、William G. Dougherty、Glenn P. A. Yap、Charles G. Riordan

  DOI：10.1021/ic900939c

  日期：2009.9.7

  The synthesis and structure of the pseudotetrahedral, sulfur-rich, high-spin organoiron(II) [phenyltris((tert-butylthio)methyl)borate]Fe(Me), [PhTt(tBu)]Fe(Me), 1, are reported. Low-temperature Mossbauer spectroscopic studies reveal an isomer shift of delta = 0.60(3) mm/s and Delta E-Q = 0.00(1) mm/s and an S = 2 ground multiplet with a negative zero-field splitting, D = -33(3) cm(-1), E/D approximate to 0.01. The small separation of the ground doublet, Delta approximate to 0.01 cm(-1), allows for observation of X-band EPR signals at g(eff) approximate to 10 (g(z) = 2.6, g(x,y) = 2.00). The relatively large negative zero-field splitting and a highly anisotropic magnetic hyperfine tensor, containing a large orbital z component, -10(4), -10(4), +33.8(2) MHz}, are concordant with the presence of unquenched orbital angular momentum. Density functional theory (DFT) calculations predict that the lowest-lying orbitals have predominantly d(xy)- and d(x2-y2)-like character, separated by an energy gap small enough to allow mixing through spin-orbit coupling, to generate a negative zero-field splitting, consistent with the experimental observations. The experimental and DFT-calculated isomer shifts are in good agreement (delta(calcd) = 0.5 mm/s). The unusual (for a high-spin ferrous site) null electric field gradients can be qualitatively explained in the frame of the spin-orbit coupling mixing. The very small Fermi contact component of the magnetic hyperfine tensor (A(FC)(exp) = -9 MHz) is not well described by the DFT approach (A(FC)(calcd) = +2 MHz). To our knowledge, this is the first study of a sulfur-coordinated high-spin organoiron(II) complex.