Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Language: Английский

Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(24)

Published: April 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Language: Английский

Challenges in the computational modelling of bimetallic C–H activation processes

Advances in organometallic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 329 - 348

Published: Jan. 1, 2024

Language: Английский