回复文章 病态晶体结构
Hong Chen1, Marilyn M Olmstead2, Richard H Fish1
1Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720, USA.
Acta crystallographica. Section C, Structural chemistry
|June 17, 2024
概括
这项研究驳斥了关于银复合物形成的说法,提供了 (I) 阴离子复合物的证据,[RhI(η1-N3-1-MT) 2]-,通过减少Cp*OH的消除.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 晶体学 晶体学是指结晶学.
背景情况:
- 之前的一项研究错误地确定了Ag{\displaystyle Ag{\displaystyle I}) 复合体,而不是预期的Rh{\displaystyle Rh{\displaystyle I}) 阴离子复合体.
- 这种错误识别源于在合成水溶性前体时使用银三酸盐 (AgOTf).
研究的目的:
- 为了使Ag (I) 复合形成的说法无效.
- 为了确认Rh(I) 阴离子成分的合成和结构,我们使用[RhI(η1-N3-1-MT) 2]-.
- 提供详细的机制解释和支持实验数据.
主要方法:
- 在特定的pH和温度条件下,[(Cp*Rh) 2(μ-OH) 3+与1-甲基乙胺 (1-MT) 的反应.
- 使用Rh(OH) 3和AgOTf与1-甲基胺的对照实验.
- 在不同的pD值和温度下在D2O中进行H NMR光谱.
- 对X射线晶体结构的分析.
主要成果:
- 证实了Rh (I) 阴离子复合体[RhI(η1-N3-1-MT) 2-的形成,Cp*OH被确定为一种减少性消除产物.
- 对照实验表明,在pH 10下,AgOTf会形成不溶性AgOH,从而排除与1-甲基乙胺的反应.
- 1H NMR光谱学证实了溶液和晶体中的结构,独立于银复合体.
结论:
- 关于Ag(I) 复合体形成的前提是无效的.
- 合成的Rh(I) 离子成分是强大的,并由光谱和结晶学证据支持.
- 介绍和验证了离子复合体形成的拟议机制.
关键词:
一个反驳的反驳.
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