针对缺氧的铜 bis ((selenosemicarbazone) 复合物:与它们的硫类似物进行比较
Thomas C Castle1, Richard I Maurer, Frank E Sowrey
1School of Physical Sciences, University of Kent, Canterbury CT2 7NR, United Kingdom.
Journal of the American Chemical Society
|August 14, 2003
概括
新的铜单半碳复合物与硫类同类物具有结构上的相似性. 电子结构计算揭示了对氧化还原性质的洞察力,这表明它有可能作为用于组织成像的放射性药物.
科学领域:
- 无机化学 无机化学
- 协调化学 协调化学
- 计算化学的计算化学
背景情况:
- 铜 bis ((thiosemicarbazone) 复合物是成熟的正方形平面化合物.
- 了解相关复合物的电子和氧化还原特性是有趣的.
- 化半巴联体为化半巴提供含的替代品.
研究的目的:
- 合成和表征第一个铜 bis ((selenosemicarbazone) 复合物.
- 与铜 bis ((thiosemicarbazone) 复合物相比,研究结构和电子上的相似性和差异.
- 使用计算方法合理化观察到的光谱和氧化还原特性.
主要方法:
- 铜 bis ((selenosemicarbazone) 复合物的合成,使用酸,pyruvaldehyde 和 2,3-butanedione bis ((selenosemicarbazone) 连接物.
- 谱学表征 (例如,UV-Vis,IR) 来确定结构和电子性质.
- 旋转不受限制的密度函数计算,以建模电子结构和合理化氧化还原行为.
主要成果:
- 铜 bis ((selenosemicarbazone) 复合物在结构上与它们的硫对应物相似.
- 用替代硫和化连接体骨干显著影响氧化和还原潜力.
- 密度函数计算表明在LUMO中存在低的基于联体的pi-orbital和d(x2)-(y2) 字符,联体pi-字符影响缩小.
- 氧化和还原涉及空间上不同的轨道,在减少的Cu (I) 物种中可能涉及连接物pi-轨道.
结论:
- 合成的铜 bis ((selenosemicarbazone) 复合体具有与铜 bis ((thiosemicarbazone) 复合体相似的结构和电子特性.
- 氧化还原潜能对连接体修饰很敏感 (S对S). Se,化),提供了对电子结构和轨道参与的见解.
- 结构和电子相似之处表明,这些铜胺基甲复合体在被标记为射质子发射铜同位素时,有可能作为用于组织 perfusion 和 hypoxia 成像的放射性药物.
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