Synthesis and Reactivity of Ampy-Based Ruthenium(II) Catalysts for Transfer Hydrogenation of Ketones

Synthesis and Reactivity of Ampy-Based Ruthenium(II) Catalysts for Transfer Hydrogenation of Ketones
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Ampy 基钌(II) 酮转移加氢催化剂的合成及反应活性

DOI:
10.1021/acs.organomet.1c00444
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发表时间:
2022
期刊:
影响因子:
2.8
通讯作者:
Ferrence, Gregory M.
Ferrence, Gregory M.
中科院分区:
化学2区
文献类型:
--
作者:
Amason, Edith K.;Rajabimoghadam, Khashayar;Baughman, Notashia N.;Ghareeb, C. Roland;Bourgeois, Samantha K.;Keuk, Channita;Manacsa, Gayle;Popp, Brian V.;Garcia-Bosch, Isaac;Ferrence, Gregory M.

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合成了4个具有顺式RuCl_2 [Ph_2P(CH_2)_4PPh_2](ampy-L)和反式RuCl_2 [Ph_2P(CH_2)_4PPh_2](ampy-L)(ampy = 2-(氨甲基)吡啶; L = Cl或OMe)的钌(II)配合物。配合物进行了充分的特点,使用NMR光谱,紫外-可见光谱,X-射线晶体学,和电化学分析。异构化反应动力学研究表明,ampy-L电子密度的微小变化并不影响反式异构化的速率。为了探索这些配合物对催化的效用,进行了各种酮的还原的转移氢化反应。所有三个顺式配合物都表现出高的速率和收率对酮转移氢化。
Four ruthenium(II) complexes of the motif,cis-RuCl2[Ph2P(CH2)4PPh2](ampy-L) andtrans-RuCl2[Ph2P(CH2)4PPh2](ampy-L) (ampy = 2-(aminomethyl)pyridine; L = Cl or OMe), were synthesized for potential catalytic applications. The complexes were fully characterized using NMR spectroscopy, UV–vis spectroscopy, X-ray crystallography, and electrochemical analyses. Thetrans-isomer was observed to undergo isomerization to thecis-isomer, and kinetic studies of the isomerization reaction showed that subtle changes in ampy-L electron density did not impact the rate oftrans-to-cisisomerization. To probe the utility of these complexes toward catalysis, transfer hydrogenation reactions were performed for the reduction of a variety of ketones. All threecis-complexes showed high rates and yields toward ketone transfer hydrogenation.
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