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Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene
Published on: July 3, 2015
用二电子减少瓦 (V) 化物以二氧化碳释放酸盐并打开协调部位
Jared S Silvia1, Christopher C Cummins
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|December 23, 2008
概括
终端化物复合物与一氧化碳的反应产生化瓦纳和酸. 该研究还描述了和异酸盐复合物,详细介绍了它们独特的氧化还原特性.
科学领域:
- 有机金属化学 有机金属化学
- 无机合成 无机合成
- 电化学 电化学 电化学
背景情况:
- 终端化物复合物是转移反应中的关键中间体.
- 了解早期过渡金属化物与小分子的反应性对于催化是至关重要的.
- 异酸盐复合物为研究金属联体氧化还原行为提供了一个平台.
研究的目的:
- 为了研究Na[NV(N[t-Bu]Ar) ((3) ]与一氧化碳的反应.
- 为了合成和结构性地描述异酸盐复合物 (OCN) V (((N[t-Bu]Ar) ((3).
- 为了比较瓦纳和同酸盐复合物的氧化还原化学.
主要方法:
- 合成Na[NV(N[t-Bu]Ar) ((3) ]和随后与CO发生反应.
- 使用NMR和IR光谱的反应产品的表征.
- (OCN) V (((N[t-Bu]Ar) ((3) 和 (OCN) Nb ((N[t-Bu]Ar) ((3) 的合成和结构性表征.
- 对异酸盐复合物的电化学研究 (循环电压测量).
主要成果:
- Na[NV(N[t-Bu]Ar) ((3) ]与二氧化碳发生反应,产生V(N[t-Bu]Ar) ((3) 和酸,分离产量为77%.
- 酸的形成通过13C标记实验得到证实.
- (OCN) V (((N[t-Bu]Ar) ((3) 在 -0.11 V 和 -1.56 V 与 Fc/Fc (((+) 相比,表现出氧化还原事件.
- (OCN) Nb ((N[t-Bu]Ar) ((3) 显示了 -1.1 V 和 -2.9 V 与 Fc/Fc ((+) 的氧化还原事件.
结论:
- 这种反应为化和酸提供了一条合成路径.
- 在和异酸复合物之间观察到减少潜力的显著差异.
- 电化学数据突出显示了这些早期过渡金属异酸盐的独特电子结构和氧化还原活性.
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