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定义一个电子氧化铜-双-氧化物复合物的电子和几何结构
Tim Storr1, Pratik Verma, Russell C Pratt
1Department of Chemistry, Stanford University, Stanford, California 94305, USA.
Journal of the American Chemical Society
|October 23, 2008
概括
铜复合物[CuSal](+) 呈现一种基于金属的氧化位点,在固体中形成Cu(III) 和溶液中的Cu(II) 与Cu(III) 之间的自旋平衡. 配体结构显著影响铜复合体中的氧化部位.
科学领域:
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
- 频谱学是一种光谱学.
背景情况:
- 具有非无害连接体的金属复合物的电子结构对于理解它们的反应性至关重要.
- 在协调化学中,区分基于金属的氧化和基于连接物的氧化是关键的挑战.
- 带有salen型联结体的铜复合体以其多样化的电子性质而闻名.
研究的目的:
- 为了研究氧化铜复合物的几何和电子结构,[CuSal](+).
- 为了确定铜复合体中氧化位置 (金属与连接体).
- 为了探索连接体结构对铜-比-氧化物复合体中氧化位点的影响.
主要方法:
- 紫外-对-红外光谱法 紫外对-红外光谱法
- 测量磁性易感度的测量方法
- 电化学 电化学 电化学
- 共振拉曼光谱法 共振拉曼光谱法
- 在X射线晶体学.
- 在X射线吸收光谱学中使用X射线吸收光谱.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 氧化铜复合物[CuSal](+) 在固态状态下完全形成一个Cu(III) 物种.
- 在溶液中,[CuSal](+) 在Cu(II) - 连接基和Cu(III) 形式之间呈现可逆自旋平衡.
- 双胺双酸连接体稳定了Cu (III) 的氧化状态,并促进了无需协调变化的自旋平衡.
- 一种相关的四氨类型,[CuSal(红色) ](+),存在于温度不变的Cu(II) - 连接基-基复合体中.
结论:
- 在[CuSal](+) 中的氧化位置主要以金属为基础,在固态中形成Cu(III).
- 溶液研究揭示了[CuSal](+) 的独特旋转平衡,表明几乎具有同能量的Cu(II) 基和Cu(III) 状态.
- 连接体设计在控制铜复合体的氧化部位和电子行为方面发挥着关键作用.
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