A redox-switchable ring-closing metathesis catalyst,Inorganic Chemistry Frontiers

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A redox-switchable ring-closing metathesis catalyst
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2017-06-13 00:00:00 , DOI: 10.1039/c7qi00018a
Dominika N. Lastovickova _{1,

2,

3,

4,

5} , Aaron J. Teator _{1,

2,

3,

4,

5} , Huiling Shao _{1,

5,

6,

7} , Peng Liu _{1,

5,

6,

7} , Christopher W. Bielawski _{1,

8,

9,

10,

11}

Affiliation

A Ru(II) complex ligated to a quinone-annulated N-heterocyclic carbene (NHC) was synthesized as a redox-active analogue of the Hoveyda–Grubbs II generation catalyst. The complex exhibited a single reversible reduction with a E_1/2 of −0.63 V (vs. SCE), and was successfully reduced and then oxidized with high fidelity using chemical reagents. While the catalyst facilitated a range of ring-closing metathesis (RCM) reactions in its neutral state, its activity was inhibited upon the introduction of a suitable reducing reagent. A series of density functional theory calculations revealed that the differences in catalytic activity may be attributed to the stronger donating ability of the reduced NHC ligand which stabilized a ruthenacyclobutane intermediate and thus suppressed the rate-determining retro-[2 + 2] cycloaddition step of the underlying RCM mechanism.

中文翻译：

可氧化还原转换的闭环复分解催化剂

连接到醌型N-杂环卡宾（NHC）的Ru（II）络合物被合成为Hoveyda-Grubbs II生成催化剂的氧化还原活性类似物。该配合物表现出单一的可逆还原，E _1/2为-0.63 V（vs。SCE），并成功还原，然后使用化学试剂高保真度氧化。尽管催化剂在中性状态下促进了一系列的闭环复分解（RCM）反应，但在引入合适的还原剂后其活性受到了抑制。一系列密度泛函理论计算表明，催化活性的差异可能归因于还原的NHC配体的较强供体能力，该配体稳定了钌烷环丁烷中间体，从而抑制了速率确定型的逆[2 + 2]环加成步骤。潜在的RCM机制。

更新日期：2017-09-12

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