| 140145-47-7

• CAS: 140145-47-7；139895-53-7
• 化学式: C₈H₂₄B₁₄Fe
• 分子量: 327.48
• InChiKey: ZZIGOAOLLZTLAZ-FTYYFIDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  三碳硼烷化学。2.钴铁和钴双（三ar硼烷）配合物的合成和结构表征

  摘要：

  A series of commo metalla bis(tricarbaborane) complexes has been generated via the reaction of the metal halide with the 6-CH3-5,6,9-C3B7H9- anion. Reaction of 6-CH3-5,6,9-C3B7H9- with FeCl2 yielded the isomeric complexes commo-Fe-(1-Fe-2-CH3-2,3,5-C3B7H9)2 (6), commo-Fe-(1-Fe-5-CH3-2,3,5-C3B7H9)2 (7), and commo-Fe-(1-Fe-5-CH3-2,3,5-C3B7H9)(1-Fe-4-CH3-2,3,4-C3B7H9) (8). Thermolysis of 6, 7, or 8 was found to produce a new isomer, commo-Fe-(1-Fe-10-CH3-2,3,10-C3B7H9)2 (9). Single-crystal X-ray determinations of 6-9 have confirmed that in each structure the iron atom is sandwiched between two tricarbon carborane cages. Compounds 6 and 7 differ in the site of substitution of the exopolyhedral methyl group. In 6 the methyl group is bound to a four-coordinate carbon as in the 6-CH3-5,6,9-C3B7H9- anion. In 7 the methyl group has rearranged to an adjacent five-coordinate cage carbon. Variable-temperature NMR studies of 7 also indicate that it is fluxional in solution. In 8, like 7, a methyl rearrangement to the five-coordinate carbon has occurred, but unlike 7, the two tricarbon carborane cages are of two different enantiomeric forms. In 9, a cage-carbon rearrangement has maximized the separation of the skeletal carbons. Although the ferratricarbaborane fragments Fe(CH3)C3B7H9 in 6-9 each exhibit gross octadecahedral geometries consistent with their closo 24-skeletal-electron counts, 6-8 also show cage distortions that result in the formation of open four-membered Fe-C-C-B faces. Reaction of 6-CH3-5,6,9-C3B7H9- with CoCl2 yielded two compounds, commo-Co-(1-Co-2-CH3-2,3,5-C3B7H9)(1-Co-5-CH3-2,3,5-C3B7H9) (10) and commo-Co-(1-Co-2-CH3-2,3,5-C3B7H9)2 (11). Both 10 and 11 are 19-electron, air-stable analogues of cobaltocene, and their structures were established by single-crystal X-ray studies. Both compounds have sandwich structures, but the cage units show cage distortions resulting in open structures that are intermediate between the normal 11-vertex 24-skeletal-electron closo and 26-skeletal-electron nido structures.

  DOI：

  10.1021/om00040a043

文献信息

• Tricarbon carborane chemistry. 1. Syntheses and structural characterizations of monocage iron, manganese, and nickel metallatricarbaborane complexes
  作者：Carole A. Plumb、Patrick J. Carroll、Larry G. Sneddon

  DOI：10.1021/om00040a042

  日期：1992.4

  Improvements in the route to the tricarbon carborane 6-CH3-5,6,9-C3B7H10 (1) and its corresponding monoanion, 6-CH3-5,6,9-C3B7H9-, have enabled the syntheses of a series of monocage iron, manganese, and nickel tricarbaborane complexes that are analogues of the cyclopentadienyl complexes of these metals. Reaction of 6-CH3-5,6,9-C3B7H9- with (eta-C5H5)Fe(CO)2I gave two isomeric products, 1-(eta-C5H5)Fe-2-CH3-2,3,4-C3B7H9 (2) and 1-(eta-C5H5)Fe-4-CH3-2,3,4-C3B7H9 (3), while reaction of the anion with Mn(CO)5Br yielded 1-(CO)3Mn-2-CH3-2,3,4-C3B7H9 (4). Single-crystal X-ray structural determinations of 2 and 3 confirm that they are hybrid complexes in which an iron atom is sandwiched between cyclopentadienyl and tricarbon carborane ligands. The ferratricarbaborane cages in both 2 and 3 have closo-octadecahedral structures, consistent with their 24-skeletal-electron counts, with the iron atom in the six-coordinate position and two of the cage carbon atoms in four-coordinate positions adjacent to the iron. The two structures differ in the position of the exopolyhedral methyl group. In 2 the methyl group is bound to a four-coordinate carbon as in 1. In 3 the methyl group has rearranged to an adjacent five-coordinate cage carbon. The reaction of 6-CH3-5,6,9-C3B7H9- with [(eta-C5H5)NiCO]2 yielded the compound 9-(eta-C5H5)Ni-8-CH3-7,8,10-C3B7H9 (5), which is proposed, on the basis of its skeletal-electron count and the spectroscopic data, to have a sandwich structure in which the nickelatricarbaborane cage has an open-cage geometry based on an icosahedron missing one vertex.