@article{10272/19704,
year = {2021},
month = {3},
url = {http://hdl.handle.net/10272/19704},
abstract = {Many transition-metal complexes MLn decompose diazo compounds N2-CR1R2 generating metal-carbenes LnM-CR1R2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR1R2 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the CR1R2 ligand has undergone a modification from the initial diazo reagent. When TpMsCu(THF) (TpMs = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N2-C(H)(CONEt2)], the stable copper carbene TpMsCu-C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as TpMsCu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C–H bonds demonstrates that the expected TpMsCu-C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.},
organization = {Funding for open access charge: Universidad de Huelva / CBUA},
organization = {Funding for open access charge: Universidad de Huelva / CBUAWe dedicate this work to the memory of Professor Victor
Riera, one of the pioneers of organometallic chemistry in
Spain. We acknowledge financial support from the Ministerio
de Ciencia e Innovación (CTQ2017-82893-C2-1-R, CTQ2017-
87792-R, P. O. Feder UHU-1260216 and P. O. Feder UHU-
1254043, and Red Intecat CTQ2016-81923-REDC)},
publisher = {American Chemical Society},
title = {Two Copper-Carbenes from One Diazo Compound},
doi = {10.1021/jacs.1c01483},
author = {Álvarez, María and Besora, María and Molina González, Francisco and Maseras, Feliu and Rodríguez Belderraín, Tomás and Pérez Romero, Pedro José},
}