的正方形平面形态复合物:合成,反应性和计算研究
Jackson A Reyna1, V Mahesh Krishnan1, Roberto Silva Villatoro1
1Department of Chemistry, University of Texas at San Antonio (UTSA), San Antonio, TX 78249, USA. zachary.tonzetich@utsa.edu.
Dalton transactions (Cambridge, England : 2003)
|July 9, 2024
概括
合成和表征了新的化物复合物. 这些复合体表现出原子转移反应性,但缺乏氨化或亚齐里迪化的催化活性,表明复杂的电子结构.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 催化剂研究 催化剂研究
背景情况:
- 复合物与基连接物对催化应用具有兴趣.
- 伊米多配体在过渡金属化学中提供独特的电子特性和反应途径.
研究的目的:
- 为了合成和表征新的四坐标像素复合物.
- 研究这些imido复合物的反应性,包括原子转移和潜在的催化应用.
- 为了探索 imido 和相关的四体复合体的电子结构.
主要方法:
- 使用亚里尔化物和PNP连接体合成化物复合物.
- 用于结构确定的X射线晶体学.
- 使用原子捐赠者的反应性研究 (TEMPOH).
- 密度函数理论 (DFT) 计算用于电子结构分析.
主要成果:
- 成功合成了四个坐标的化物复合物 [Co(NAr) ((PNP) ] .
- 观察到不寻常的正方形平面几何形状和近乎线性的 imido 单位.
- 证明了从TEMPOH的原子转移到imido,形成amido复合体.
- 没有发现C-H氨基化或亚齐里丁化与测试基质的催化活性.
- 合成了一种带有过量亚酸的四化物复合物[Co(N4Ph2) ((PNP) ].
- DFT计算表明,一个低旋转的(II) 离子与一个 iminyl 基结合在一起.
结论:
- 合成的化物复合体表现出有趣的结构和电子特性.
- 虽然它们能够转移H原子,但它们不能催化C-H氨化或亚齐里迪化.
- 电子结构涉及一个 (II) 基性质,影响它们的反应性.
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