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• W2761783616 abstract "The cleavage of aromatic carbon-nitrogen bonds catalyzed by transition metals is of high synthetic interest because such bonds are common in organic chemistry. However, few metal catalysts can be used to selectively break C(aryl)-N bonds in electronically neutral molecules. We report here the first low-valent, high-spin chromium-catalyzed cleavage of C(aryl)-N bonds in electronically neutral aniline derivatives at room temperature. By using simple and inexpensive chromium(II) chloride as precatalyst, accompanied by an imino auxiliary, the selective arylative and alkylative C-C coupling of C(aryl)-N bonds can be achieved. Crossover experiments indicate that a low-valent chromium species, formed in situ by reduction of CrCl2 with Grignard reagent, is responsible for the catalytic cleavage of C(aryl)-N bonds. DFT calculations show that facile insertion of the C(aryl)-N bond by chromium(0) can take place in a high-spin quintet (S = 2) ground state, whereas the lower-spin singlet (S = 0) and triplet (S = 1) states are inaccessible in energy. It was found that both donation of the sole paired d electrons in the d6 shell of high-spin chromium(0) to the antibonding orbital of the C(aryl)-N bond and the nitrogen ligating interaction to the metal center with its lone pair play important roles in the cleavage of the C(aryl)-N bond by the zerovalent chromium species." @default.
• W2761783616 created "2017-10-20" @default.
• W2761783616 creator A5011090841 @default.
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• W2761783616 creator A5042551529 @default.
• W2761783616 creator A5076012285 @default.
• W2761783616 date "2017-10-12" @default.
• W2761783616 modified "2023-10-13" @default.
• W2761783616 title "Low-Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic Carbon–Nitrogen Bonds at Room Temperature: A Combined Experimental and Theoretical Study" @default.
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• W2761783616 doi "https://doi.org/10.1021/jacs.7b08579" @default.
• W2761783616 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/28972750" @default.
• W2761783616 hasPublicationYear "2017" @default.
• W2761783616 type Work @default.

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