Csp2-H/F 键活化和与铁的硼酸化作用。

IF 4.3 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemical Communications Pub Date : 2024-11-18 DOI:10.1039/d4cc04127e

Ethan Zars, Lisa Pick, Achala Kankanamge, Michael R Gau, Karsten Meyer, Daniel J Mindiola

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引用次数: 0

摘要

在冠醚 18-C-6 的存在下，[K2{(tBupyrr2pyr)Fe}2(μ-N2)] (1) 与两个等量的 KC8 还原，生成 N2 加合物 [{K(18-C-6)}2(tBupyrr2pyr)Fe(N2)] (2)。配合物 2 可异质裂解苯的 Csp2-H 键，形成 [{K(18-C-6)}(tBupyrr2pyr)Fe(C6H5)] (3)，二硼 B2pin2 的使用可促进氢化物消除，形成盐 [K(18-C-6)HB2Pin2] (4)。同样，3 也可以通过裂解氟苯的 C-F 键形成。3 与 ClBcat 反应生成[K(18-C-6)(thf)2][(tBupyrr2pyr)FeCl] (5) 和 PhBcat，前者可还原成 2，从而完成异溶性苯 C-H 活化和硼酸化的合成循环。

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C_sp²-H/F bond activation and borylation with iron.

Reduction of [K₂{(^tBupyrr₂pyr)Fe}₂(μ-N₂)] (1) with two equiv. of KC₈ in the presence of crown-ether 18-C-6 yields the N₂ adduct [{K(18-C-6)}₂(^tBupyrr₂pyr)Fe(N₂)] (2). Complex 2 heterolytically splits the C_sp²-H bond of benzene to form [{K(18-C-6)}(^tBupyrr₂pyr)Fe(C₆H₅)] (3), whereby usage of a diboron B₂pin₂ promotes hydride elimination to form the salt [K(18-C-6)HB₂Pin₂] (4). Similarly, 3 can also be formed by cleavage of the C-F bond of fluorobenzene. Reaction of 3 with ClBcat yields [K(18-C-6)(thf)₂][(^tBupyrr₂pyr)FeCl] (5) and PhBcat and the former can be reduced to 2 to complete a synthetic cycle for heterolytic benzene C-H activation and borylation.

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来源期刊

Chemical Communications 化学-化学综合

CiteScore

8.60

自引率

4.10%

发文量

2705

审稿时长

1.4 months

期刊介绍： ChemComm (Chemical Communications) is renowned as the fastest publisher of articles providing information on new avenues of research, drawn from all the world''s major areas of chemical research.