5,6-CH2OCH2-5,6-C2B8H10 | 905921-34-8

• 英文名称: 5,6-CH2OCH2-5,6-C2B8H10
• CAS: 905921-34-8
• 化学式: C₄H₁₄B₈O
• 分子量: 164.643
• InChiKey: MTEZKXZPIJFWCI-VKHMYHEASA-N

反应信息

• 作为反应物：
  描述：

  5,6-CH2OCH2-5,6-C2B8H10 、 异氰酸叔丁酯 、 四丁基溴化铵 在 1,8-bis(dimethylamino)naphthalene 作用下， 以 二氯甲烷 为溶剂， 以44%的产率得到Bu4N[7,8-CH2OCH2-9-tert-BuNH-7,8,9-C3B8H8]
  参考文献：
  名称：

  A restricted polyhedral rearrangement of an aminosubstituted 12-vertex ferratricarbollide

  摘要：

  The oxidation of anion [7,8-CH2OCH2-7,8-C2B9H10](-) with aqueous FeCl3 gives the 10-vertex nido-carborane 5,6-CH2OCH2-5,6-C2B8H10 in 23% yield. Its interaction with BuNC in the presence of proton sponge gives the tricarbollide anion [7,8-CH2OCH2-9Bu(t)NH-7,8,9-C3B8H8](-) (44% yield) having a short linkage between carbon atoms. Further photochemical reaction of this anion with [CpFe(C6H6)](+) is accompanied by room-temperature polyhedral rearrangement giving ferratricarbollide 1-Cp-2,3-CH2OCH2-9-(BuNH)-N-t-1,2,3,9-FeC3B8H8 (5) in 89% yield. The process involves the migration of the amino-substituted carbon atom, while the separation of two other carbons (observed for the non-linked analogue) is restricted by the CH2OCH2 bridge. DFT calculations of the hypothetical non-rearranged isomer 1-Cp-2-(BuNH)-N-t-1,2,3,4-FeC3B8H10 revealed its strongly distorted geometry with the C2-C3 distance (2.347 angstrom) being clearly non-bonding, thus explaining the mild conditions of the polyhedral rearrangement. The structure of 5 was confirmed by X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.03.007
• 作为产物：
  描述：

  K[7,8-CH2OCH2-7,8-C2B9H10] 在 FeCl₃*6H₂O 、 HCl 作用下， 以 正己烷 、 水 为溶剂， 以23%的产率得到5,6-CH2OCH2-5,6-C2B8H10
  参考文献：
  名称：

  A restricted polyhedral rearrangement of an aminosubstituted 12-vertex ferratricarbollide

  摘要：

  The oxidation of anion [7,8-CH2OCH2-7,8-C2B9H10](-) with aqueous FeCl3 gives the 10-vertex nido-carborane 5,6-CH2OCH2-5,6-C2B8H10 in 23% yield. Its interaction with BuNC in the presence of proton sponge gives the tricarbollide anion [7,8-CH2OCH2-9Bu(t)NH-7,8,9-C3B8H8](-) (44% yield) having a short linkage between carbon atoms. Further photochemical reaction of this anion with [CpFe(C6H6)](+) is accompanied by room-temperature polyhedral rearrangement giving ferratricarbollide 1-Cp-2,3-CH2OCH2-9-(BuNH)-N-t-1,2,3,9-FeC3B8H8 (5) in 89% yield. The process involves the migration of the amino-substituted carbon atom, while the separation of two other carbons (observed for the non-linked analogue) is restricted by the CH2OCH2 bridge. DFT calculations of the hypothetical non-rearranged isomer 1-Cp-2-(BuNH)-N-t-1,2,3,4-FeC3B8H10 revealed its strongly distorted geometry with the C2-C3 distance (2.347 angstrom) being clearly non-bonding, thus explaining the mild conditions of the polyhedral rearrangement. The structure of 5 was confirmed by X-ray diffraction. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.03.007