7-N,7-N,8-N,8-N-tetramethyl-3,12-dithia-7,8-diboratricyclo[7.3.0.02,6]dodeca-1(9),2(6),4,10-tetraene-7,8-diamine | 1180677-12-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 7-N,7-N,8-N,8-N-tetramethyl-3,12-dithia-7,8-diboratricyclo[7.3.0.02,6]dodeca-1(9),2(6),4,10-tetraene-7,8-diamine
• CAS: 1180677-12-6
• 化学式: C₁₂H₁₆B₂N₂S₂
• 分子量: 274.026
• InChiKey: VBWIUZDELPOVRT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.09
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  63
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7-N,7-N,8-N,8-N-tetramethyl-3,12-dithia-7,8-diboratricyclo[7.3.0.02,6]dodeca-1(9),2(6),4,10-tetraene-7,8-diamine 在 lithium 作用下， 以 氘代四氢呋喃 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  A B−B Bond-Containing Polycyclic π-Electron System: Dithieno-1,2-dihydro-1,2-diborin and Its Dianion

  摘要：

  As a B-B bond-containing polycyclic pi-electron system, a dithieno[3,2-c:2',3'-e](1,2-dihydro-1,2-diborin) derivative and its dianion salts were successfully prepared, and their structures were determined by X-ray crystallography. The neutral. dithieno-1,2dihydro-1,2-diborin has a twisted diborin ring in which both the sigma-TT and p-pi* orbital interactions between the bithiophene pi framework and the B-B bond moiety effectively take place, giving rise to an absorption that is significantly red-shifted compared with that of the parent bithiophene. Upon a two-electron reduction, the dithienodiborin pi framework becomes planar and has a characteristic peripheral. pi conjugation through the B-B bond with 14 pi etectrons. Furthermore, the dianion salts show an intriguing countercation effect on their photophysical, properties, indicative of possible etectronic tuning by the countercations.

  DOI：

  10.1021/ja905007s
• 作为产物：
  描述：

  3,3'-二溴-2,2'-联噻吩 、 1,2-dibromo-1,2-bis(dimethylamino)diborane 在 正丁基锂 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 17.0h， 以32%的产率得到7-N,7-N,8-N,8-N-tetramethyl-3,12-dithia-7,8-diboratricyclo[7.3.0.02,6]dodeca-1(9),2(6),4,10-tetraene-7,8-diamine
  参考文献：
  名称：

  A B−B Bond-Containing Polycyclic π-Electron System: Dithieno-1,2-dihydro-1,2-diborin and Its Dianion

  摘要：

  As a B-B bond-containing polycyclic pi-electron system, a dithieno[3,2-c:2',3'-e](1,2-dihydro-1,2-diborin) derivative and its dianion salts were successfully prepared, and their structures were determined by X-ray crystallography. The neutral. dithieno-1,2dihydro-1,2-diborin has a twisted diborin ring in which both the sigma-TT and p-pi* orbital interactions between the bithiophene pi framework and the B-B bond moiety effectively take place, giving rise to an absorption that is significantly red-shifted compared with that of the parent bithiophene. Upon a two-electron reduction, the dithienodiborin pi framework becomes planar and has a characteristic peripheral. pi conjugation through the B-B bond with 14 pi etectrons. Furthermore, the dianion salts show an intriguing countercation effect on their photophysical, properties, indicative of possible etectronic tuning by the countercations.

  DOI：

  10.1021/ja905007s

文献信息

• Antiaromatic Dithieno-1,2-dihydro-1,2-diborin Splits Diatomic Hydrogen
  作者：Takafumi Araki、Masato Hirai、Atsushi Wakamiya、Warren E. Piers、Shigehiro Yamaguchi

  DOI：10.1246/cl.170812

  日期：2017.12.5

  B,B-Dimesityl-substituted dithieno-1,2-dihydro-1,2-diborin was synthesized and its properties and reactivity were studied. Owing to the noticeably electron-deficient and antiaromatic character of the 1,2-dihydro-1,2-diborin ring, this compound was found to homolytically cleave diatomic hydrogen (H2) gas at ambient temperature under 1 atm to afford a hydrogen-bridged bis(borane). This reaction was accompanied by a dramatic color change from dark green to yellow in addition to a turn-on fluorescence response.

  研究人员合成了 B,B-二美司基取代的二噻吩-1,2-二氢-1,2-二硼烷基化合物，并对其性质和反应活性进行了研究。由于 1,2-二氢-1,2-二硼烷环具有明显的缺电子和反芳香族特性，研究发现这种化合物在 1 atm 的环境温度下会均聚裂解二原子氢（H2）气体，生成氢桥双硼烷。该反应伴随着颜色从深绿色到黄色的剧烈变化以及荧光开启反应。