化学可逆的四电子氧化和还原利用两个无机功能组
Michael Nippe1, Samuel M Goodman, Charles G Fry
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
Journal of the American Chemical Society
|February 16, 2011
概括
一种新的氧化合物表现出可逆的四电子反应,与惰性单核物种不同. 这种反应性源于在ditungsten复合体中的合作性W-O和W-W多重结合.
科学领域:
- 无机化学 无机化学 有机化学
- 有机金属化学 有机金属化学
- 材料科学 材料科学 材料科学
背景情况:
- 单核氧物种通常是化学惰性的.
- 四重结合的双核化合物具有独特的反应性.
- 了解多电子还氧化过程对于催化和材料至关重要.
研究的目的:
- 为了合成和表征一种新型的dithungsten终端氧化合物.
- 为了研究新化合物的氧化还原行为和化学反应性.
- 探索合作性多重结合在观察到的反应性中的作用.
主要方法:
- 合成四重结合的W(2)(II,II) 前体.
- 通过四电子氧化,形成了无的终端氧化合物.
- 在乙尼中使用tri-tert-butylphosphine进行四电子还原.
主要成果:
- 形成了一种新型的,二磁性双末端氧化化合物[W(2) O(2,2'-二氧化胺) ((4) ] ((2+).
- 这种氧化合物经历了一种简单的四电子还原与氧原子转移.
- 原始的双核前体W(2)(2,2'-二氧化胺)(4) 被回收,证明了化学可逆性.
结论:
- 合成的丁氧化合物表现出异常的,化学可逆的多电子反应性.
- 这种反应性归因于W-O和W-W多重键的协同效应.
- 这些发现挑战了氧物种的一般惰性,并突出了合作性结合.
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