期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 12, 页码 4897-4901出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201916073
关键词
aluminium; aluminyl reagent; carbon monoxide; imide; small molecule activation
资金
- Leverhulme Trust [F/08699/E]
- Academy of Finland [314794]
- Academy of Finland (AKA) [314794, 314794] Funding Source: Academy of Finland (AKA)
Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K-2[(NON)Al(NDipp)](2) (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al-N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate leads to C-C coupling and C equivalent to O bond cleavage. Thermodynamically, this is driven, at least in part, by Al-O bond formation. Mechanistically, a combination of quantum chemical and experimental observations suggests that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium-bound isocyanate fragment.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据