dc.contributor.author |
Álvarez, María |
dc.contributor.author |
Besora, Maria |
dc.contributor.author |
Molina, Francisco |
dc.contributor.author |
Maseras Cuní, Feliu |
dc.contributor.author |
Belderrain, Tomás R. |
dc.contributor.author |
Pérez, Pedro J. |
dc.date |
2021 |
dc.date.accessioned |
2022-10-30T13:29:06Z |
dc.date.available |
2022-10-30T13:29:06Z |
dc.date.issued |
2022-10-30 |
dc.identifier |
https://ddd.uab.cat/record/250415 |
dc.identifier |
urn:10.1021/jacs.1c01483 |
dc.identifier |
urn:oai:ddd.uab.cat:250415 |
dc.identifier |
urn:pmcid:PMC8603358 |
dc.identifier |
urn:pmc-uid:8603358 |
dc.identifier |
urn:pmid:33733762 |
dc.identifier |
urn:articleid:15205126v143p4837 |
dc.identifier |
urn:oai:pubmedcentral.nih.gov:8603358 |
dc.identifier.uri |
http://hdl.handle.net/2072/524336 |
dc.format |
application/pdf |
dc.language |
eng |
dc.publisher |
|
dc.relation |
Agencia Estatal de Investigación CTQ2017-87792-R |
dc.relation |
Agencia Estatal de Investigación CTQ2017-82893-C2-1-R |
dc.relation |
Ministerio de Economía y Competitividad CTQ2016-81923-REDC |
dc.relation |
Journal of the American Chemical Society ; Vol. 143 (March 2021), p. 4837-4843 |
dc.rights |
open access |
dc.rights |
Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original. |
dc.rights |
https://creativecommons.org/licenses/by/4.0/ |
dc.title |
Two Copper-Carbenes from One Diazo Compound |
dc.type |
Article |
dc.description.abstract |
Many transition-metal complexes ML decompose diazo compounds N=CR 1 R 2 generating metal-carbenes LM=CR 1 R 2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR 1 R 2 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 CR 1 R 2 ligand has undergone a modification from the initial diazo reagent. When Tp Ms Cu(THF) (Tp Ms = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N -diethyl diazoacetamide [N=C(H)(CONEt)], the stable copper carbene Tp Ms Cu=C(H)(NEt) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as Tp Ms Cu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected Tp Ms Cu=C(H)(CONEt) 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. |