三坐标的降解功率 (I)
Michael J Ingleson1, Maren Pink, Kenneth G Caulton
1Department of Chemistry, Indiana University, Bloomington, 47405-7102, USA.
Journal of the American Chemical Society
|March 30, 2006
概括
有PNP连接体的复合物很容易与一氧化碳结合,表明容易氧化的 (I) 中心. 然而,完全氧化成 (III) 是具有挑战性的,中间物种形成.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 无机合成 无机合成
背景情况:
- 低价值过渡金属复合物的反应性对于催化和材料科学至关重要.
- 复合物,特别是联体,由于其多样化的氧化状态和结合能力,引起了人们的兴趣.
- 了解复合物的电子特性和氧化途径,有助于设计新的功能分子.
研究的目的:
- 研究由庞大的PNP连接体支的复合物的协调化学和氧化行为.
- 为了描述与一氧化碳和氧化剂反应后形成的产品.
- 为了探索这种特定的连接体环境中的氧化极限.
主要方法:
- (PNP) Co复合物的合成和特征.
- 红外光谱学用于研究一氧化碳协调.
- 与 (I2) 和一种二化合物 (N2CH(SiMe3)) 发生反应,以探测氧化.
- 进行X射线晶体学以确定反应产物的结构.
主要成果:
- 在 (PNP) Co中添加一氧化碳,产生 (PNP) Co (CO),核值为1885 cm-1,表明显著的反捐和容易氧化的Co (I) 中心.
- (PNP) Co与I2的氧化不会导致稳定的Co(III) 物种;相反, (PNP) CoI和一个zwitterionic Co(III) 复合体,[ItBu2PCH2SiMe2NSiMe2CH2PtBu2]CoI2形成.
- 与N2CH(SiMe3) 发生反应,产生1:1的附加物,其晶体结构表明Co(I的部分氧化,而不是完全的Co(III) 状态.
结论:
- 重的PNP连接体稳定了容易氧化的Co (I) 状态,促进了CO结合.
- 中心能够进入更高的氧化状态,如Co(III),由PNP连接体和反应条件在固态和电子上受到限制.
- 观察到的反应性突出显示了在有机金属化学中,通过量身定制的配体设计可以实现对氧化还原性质的细微控制.
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