Reversible Reductive Elimination in Aluminum(II) Dihydrides.

Reversible Reductive Elimination in Aluminum(II) Dihydrides.
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DOI:
10.1002/anie.202011418
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发表时间:
2021-01-25
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Cowley MJ
Cowley MJ
中科院分区:
其他
文献类型:
--
作者:
Falconer RL;Nichol GS;Smolyar IV;Cockroft SL;Cowley MJ

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氧化加成和还原消除是过渡金属有机金属化学的定义反应。在主族化学中,氧化加成反应现已十分成熟,但还原消除反应尚未以同样的方式普遍化。在此,我们报道了由酰胺基膦配体支持的二氢二烷。该配体充当涉及 AlI 和 AlIII 中间体的可逆还原消除/氧化加成化学的立体化学报告分子。低氧化态主族化合物表现出丰富的氧化加成化学。对于相反的过程,即还原消除,情况并非如此。总而言之,这些过程可以在过渡金属化学中实现大量的催化循环。在这里,使用立体活性配体作为报告基因,揭示了 AlII 二氢二烷表现出类过渡金属的可逆还原消除。 Mes=2,4,6-三甲基苯基。
Oxidative addition and reductive elimination are defining reactions of transition‐metal organometallic chemistry. In main‐group chemistry, oxidative addition is now well‐established but reductive elimination reactions are not yet general in the same way. Herein, we report dihydrodialanes supported by amidophosphine ligands. The ligand serves as a stereochemical reporter for reversible reductive elimination/oxidative addition chemistry involving AlI and AlIII intermediates. Low‐oxidation‐state main‐group compounds exhibit rich oxidative addition chemistry. The same is not true for the reverse process, reductive elimination. Put together, the processes enable numerous catalytic cycles in transition‐metal chemistry. Here, using a stereoactive ligand as a reporter, it is revealed that AlII dihydrodialanes exhibit transition‐metal‐like reversible reductive elimination. Mes=2,4,6‐trimethylphenyl.
DOI: 10.1021/acs.inorgchem.9b01061
发表时间: 2019-09-02
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