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Synthesis of a Water-soluble Metal–Organic Complex Array
Published on: October 8, 2016
循环和开放性臭氧和硫的过渡金属复合物
Beate Flemmig1, Peter T Wolczanski, Roald Hoffmann
1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853-1301, USA.
Journal of the American Chemical Society
|January 27, 2005
概括
研究人员探索了在过渡金属复合体中捕获周期性臭氧 (O3) 和硫 (S3). 计算方法表明具有特定连接体的稳定复合体,为研究这些难以捉摸的分子提供了新的途径.
科学领域:
- 无机化学 无机化学
- 计算化学的计算化学
- 有机金属化学 有机金属化学
背景情况:
- 循环臭氧 (O3) 和循环硫 (S3) 是具有预测动力稳定性的价值异电子分子,但尚未在实验中分离出来.
- 过渡金属复合物为稳定和研究这些反应性物种提供了潜在的途径.
研究的目的:
- 通过将它们与过渡金属复合,研究合成和分离循环臭氧 (O3) 和循环硫 (S3) 的可行性.
- 为了确定合适的过渡金属碎片和能够稳定这些循环三原子物种的配体.
主要方法:
- 利用18电子规则指导构建潜在的过渡金属复合体候选者.
- 使用密度函数理论 (DFT) 与B3LYP函数用于结构优化和电子分析.
- 探索了各种粘合模式 (二位数,pi,eta1,eta2,eta3) 和过渡金属中心的复合体.
主要成果:
- 确定了几种可能的结构,包括oxo-peroxo物种,开放的臭氧复合体和eta1/eta2循环臭氧复合体.
- 发现了由过渡金属碎片稳定起来的真实的eta3循环O3和S3复合体,特别是那些具有强大的pi-接受器连接物,如酸 (NO).
- 提出的特定复杂配方,如[S3W(NO) ]3+,[O3M(NO) ]3+ (M = Cr, Mo, W, Fe, Ru, Os),[S3W(NO) ]2+,[S3M(NO) ]3+ (M = Cr, Mo, W, Fe, Ru, Os) 等.
结论:
- 这项研究表明,循环臭氧和硫臭氧可以在特定的过渡金属复合体内动态稳定.
- 使用强大的pi-接受器连接体,如化,对于最小化能量不匹配和促进复杂的形成至关重要.
- 这些发现为新型循环O3和S3复合物的实验合成提供了理论基础.
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