iron(2,6-xylyl-isocyanide)3(i-Pr-DAB) | 141647-13-4

• 英文名称: iron(2,6-xylyl-isocyanide)3(i-Pr-DAB)
• CAS: 141647-13-4
• 化学式: C₃₅H₄₃FeN₅
• 分子量: 589.607
• InChiKey: YLCGOPNZRGLAMC-BEHGBPRGSA-N

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

• 作为反应物：
  描述：

  iron(2,6-xylyl-isocyanide)3(i-Pr-DAB) 在 carbon disulfide 作用下， 以 正戊烷 为溶剂， 以80%的产率得到iron(2,6-xylyl-isocyanide)3(iPrNCHC(CSS)N(iPr)CN-2,6-xylyl)
  参考文献：
  名称：

  1，3-偶极环加成到FeN= C片段XII°。的Fe（2,6-二甲苯基胩）的反应性的3（我镨-α二亚胺）朝向heteroallenic C = S键

  摘要：

  Fe（2,6-xylylNC）3（i Pr-DAB）（5）与二硫化碳和羰基硫的反应产生双环结构。与二硫化碳的反应是通过Fe = N = C单元上的C = S键的1,3-偶极环加成进行的，然后进行异氰酸酯插入形成ferra [2.2.2]双环配合物（8）。（8）上的单晶X射线结构测定）显示它包含三个六元环；二硫化碳通过硫原子与中心金属原子相连，并通过其中心碳原子与前亚胺碳原子相连。在羰基硫的1，3-偶极环加成反应中，水分的存在会导致酰胺官能团的质子化。这抑制了异氰酸酯的插入并稳定了最初形成的ferra [2.2.1]-双环化合物。

  DOI：

  10.1016/0022-328x(94)87061-6
• 作为产物：
  描述：

  以 氘代甲苯 为溶剂， 生成 iron(2,6-xylyl-isocyanide)3(i-Pr-DAB)
  参考文献：
  名称：

  1,3-Dipolar Cycloaddition to the Fe-N:C Fragment. 14. Aromatic Isothiocyanates as Dipolarophiles. Reversible Formation of Novel [3.2.2] Bicyclic Double Isocyanide Insertion Products. Thermodynamics of Isocyanide Deinsertion Reactions

  摘要：

  The 1,3-dipolar cycloaddition reaction of Fe((2,6-xylyl)NC)3(i-PrDAB) (7) with para-substituted phenyl isothiocyanates (R''C6H4NCS; R'' = H (a), Me (b), OMe (c), NO2 (d)) is followed by one or two isonitrile insertions. Depending on the solvent and type of isothiocyanate used, [2.2.2] and [3.2.2] bicyclic products (10 and 11) are isolated. Crystals of 10a, C51H57N7SFe, are monoclinic, space group I2/a, with cell constants a = 24.041(2) angstrom, b = 12.095(2) angstrom, c = 36.161(6) angstrom, V = 10502(3) angstrom3, Z = 8, and R = 0.109 for 2918 observed reflections with I > 2.5sigma(I). Compounds 11 undergo a unique reversible isocyanide deinsertion reaction when warmed in toluene. The equilibria 11a-d reversible 10a-d + 2,6-xylyl-NC have been studied by H-1 NMR. The equilibrium constants at various temperatures (303 K less-than-or-equal-to T less-than-or-equal-to 368 K) have been determined from which for the first time DELTAG-degrees (a, 16.2 +/- 2.7; b, 22.7 +/- 1.6; c, 23.2 +/- 1.9; d, 24.7 +/- 1.1 kJ/mol), DELTAH-degrees (a, 61.6 +/- 6.3; b, 74.5 +/- 3.3; c, 65.5 +/- 2.0; d, 86.9 +/- 2.5 kJ/mol), and DELTAS-degrees (a, 152 +/- 29; b, 174 +/- 14; c, 142 +/- 12; d, 208 +/- 11 J/(mol.K)) values could be calculated for isocyanide deinsertion. These values provide an explanation for the observed product selectivities in different solvents. The reactions 7 reversible 10 are also reversible; however equilibrium constants could not be determined because at the required temperatures compound 7 is itself too labile.

  DOI：

  10.1021/om00019a044

文献信息

• 1,3-Dipolar cycloaddition to the Fe-N:C fragment. 11. Isocyanide-controlled change between a reversible molecular self-assembly of three components, including a unique isocyanide deinsertion, and dimethyl maleate coupling reactions
  作者：Paul P. M. De Lange、Rene P. De Boer、Maarten Van Wijnkoop、Jan M. Ernsting、Hans Werner Fruhauf、Kees Vrieze、Wilberth J. J. Smeets、Anthony L. Spek、Kees Goubitz

  DOI：10.1021/om00026a031

  日期：1993.2

  In the reaction of Fe(CNR)3(i-Pr-alpha-diimine) (6; R = 2,6-xylyl (a), t-Bu (b), c-Hex (c)) with dimethyl maleate, two totally different pathways are followed, depending on the type of isocyanide used. With the aromatic isocyanide, a 1,3-dipolar cycloaddition of the alkene to the Fe-N=C unit occurs followed by an isocyanide insertion, forming a ferra [2.2.2] bicyclic compound (7a). When this mixture is warmed above room temperature, the reaction is reversed, disasseebling 7a into its starting components. During this facile retro-cycloaddition, C-C, C-N, and Fe-C bonds are broken. Also, the first unambiguous example of an isocyanide deinsertion is encountered. The starting complexes 6b,c, with aliphatic isocyanides, react with dimethyl maleate to give two products. The first, a purely organic product (8), is a dimer of two coupled alkenes. The second product is the organometallic tricyclic complex Fe(CNR)3(tric) (9b,c), in which two alkenes are coupled and bonded to the metal and the alpha-diimine ligand. In the cyclization reaction, a gamma-lactam ring is formed and a methoxy group of one of the four ester groups is removed, with formation of methanol. The molecular structure of the [2.2.2] bicyclic complex 7a (FeC50H60N6O4, triclinic, space group P1BAR, a = 10.367 (1) angstrom, b = 14.615 (3) angstrom, c = 15.787 (2) angstrom, alpha = 95.78 (2)-degrees, beta = 96.62 (1)-degrees, gamma = 92.21 (1)-degrees, Z = 2, R = 0.053, R(w) = 0.055) consists of three six-membered rings with the metal in a bridgehead position. The single-crystal X-ray structure of the organic dimer 8 (C12H16O8, monoclinic, space group A2/a, a = 8.291 (2) angstrom, b = 8.291 (2) angstrom, c = 20.551 (2) angstrom, beta = 96.09 (1)-degrees, Z = 4, R = 0.068, R(w) = 0.089) reveals a symmetric alkene. The molecular structure of the Fe(t-BuNC)3(tric) species 9b (FeC34H55N5O7.0.5CH2-Cl2.0.5C4H10O, monoclinic, space group Pc, a = 11.201 (1) angstrom, b = 12.251 (2) angstrom, c = 32.019 (3) angstrom, beta = 96.43 (1)-degrees, Z = 4, R = 0.0581, R(w) = 0.0629) consists of a four-, a five-, and a six-membered ring. The metal is incorporated in the six- and the four-membered rings.
• Molecular self assembly: temperature controlled reversible formation of a bicyclo[2.2.2]organoiron complex via consecutive organometal 1,3-dipolar cycloaddition and isocyanide insertion reactions
  作者：René P. de Boer、Paul P. M. de Lang、Hans-Werner Frühauf、Kees Vrieze

  DOI：10.1039/c39920000580

  日期：——

  In a unique temperature dependent reversible reaction, the bicyclo[2.2.2]organoiron complex 8 is assembled from three molecular components, i.e. the Fe(CNR)3(alpha-diimine) complex 1b, dimethyl maleate and 2,6-xylyl isocyanide, and disassembled again via consecutive organometal 1,3-dipolar concerted cycloaddition-reversion and isocyanide insertion-deinsertion reactions.
• De Lange, Paul P. M.; Van Wijnkoop, Maarten; Frühauf, Hans-Werner, Organometallics, 1993, vol. 12, # 2, p. 428 - 439
  作者：De Lange, Paul P. M.、Van Wijnkoop, Maarten、Frühauf, Hans-Werner、Vrieze, Kees、Goubitz, Kees

  DOI：——

  日期：——