RT info:eu-repo/semantics/article
T1 Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights
A1 Logallo, Alessandra
A1 Maddock, Lewis C. H.
A1 Mu, Manting
A1 Gravogl, Lisa
A1 Jin, Na
A1 Peñas de Frutos, Marconi Nicolás
A1 Karsten, Meyer
A1 García Melchor, Max
A1 Hevia, Eva
K1 Amide
K1 Cobalt
K1 Fluoroarenes
K1 Iron
K1 Metalation
K1 2303 Química Inorgánica
AB 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 metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth-abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M−H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C-H metalation occurs leaving C−F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions.
PB Wiley-VCH GmbH
SN 1433-7851
YR 2024
FD 2024
LK https://uvadoc.uva.es/handle/10324/67702
UL https://uvadoc.uva.es/handle/10324/67702
LA eng
NO Angewandte Chemie International Edition, april 2024, e202402907
NO Producción Científica
DS UVaDOC
RD 17-jul-2024