How Does Iridium(III) Photocatalyst Regulate Nickel(II) Catalyst in Metallaphotoredox-Catalyzed C-S Cross-Coupling? Theoretical and Experimental Insights

doi:10.1021/acscatal.9b00375

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	How Does Iridium(III) Photocatalyst Regulate Nickel(II) Catalyst in Metallaphotoredox-Catalyzed C-S Cross-Coupling? Theoretical and Experimental Insights
	H.Ren; G.F.Li; B.Zhu; X.D.Lv; L.S.Yao; X.L.Wang; Z.M.Su
刊名	Acs Catalysis
	2019
卷号	9 期号:5 页码:3858-3865
关键词	C-S cross-coupling,photoredox catalysis,iridium,nickel,density,functional calculations,Chemistry
ISSN号	2155-5435
DOI	10.1021/acscatal.9b00375
英文摘要	Photoredox-mediated iridium/nickel dual catalysis has successfully triggered a series of traditionally challenging carbon-heteroatom cross-coupling reactions. However, detailed mechanisms, such as the catalytic cycles for dual catalysts and the role of base additive, remain controversy in these reactions. In this study, a highly chemoselective C-S cross-coupling of thiols with heteroaryl iodides has been investigated by density functional theory (DFT) calculations and emission quenching experiments. Interestingly, the oxidation state modulation mechanism merging oxidative quenching (Ir-III-Ir-III-Ir-IV-Ir-III) and nickel catalytic cycles (Ni-II-Ni-I-Ni-III-Ni-I-Ni-II) is favorable. It is consisted of four major steps: pyridine mediated proton-coupled electron transfer, oxidative addition Ni(I)-halide complex, reductive elimination, and single-electron transfer. In contrast, the radical by reductive quenching of Ir-III with thiols is impractical, because oxidative addition or sigma-bond metathesis from Ni(II)-thiolate intermediate is highly energy-demanding. This study will hopefully benefit the future understanding of such photoredox-mediated dual catalytic systems.
语种	英语
内容类型	期刊论文
源URL	[http://ir.ciomp.ac.cn/handle/181722/63091]
专题	中国科学院长春光学精密机械与物理研究所
推荐引用方式 GB/T 7714	H.Ren,G.F.Li,B.Zhu,et al. How Does Iridium(III) Photocatalyst Regulate Nickel(II) Catalyst in Metallaphotoredox-Catalyzed C-S Cross-Coupling? Theoretical and Experimental Insights[J]. Acs Catalysis,2019,9(5):3858-3865.
APA	H.Ren.,G.F.Li.,B.Zhu.,X.D.Lv.,L.S.Yao.,...&Z.M.Su.(2019).How Does Iridium(III) Photocatalyst Regulate Nickel(II) Catalyst in Metallaphotoredox-Catalyzed C-S Cross-Coupling? Theoretical and Experimental Insights.Acs Catalysis,9(5),3858-3865.
MLA	H.Ren,et al."How Does Iridium(III) Photocatalyst Regulate Nickel(II) Catalyst in Metallaphotoredox-Catalyzed C-S Cross-Coupling? Theoretical and Experimental Insights".Acs Catalysis 9.5(2019):3858-3865.