Author, as appears in the article.: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.;
Department: Química Física i Inorgànica
e-ISSN: 1520-5126
URV's Author/s: Besora Bonet, Maria
Keywords: Transition metals Synthesis (chemical) Simultaneous observation Reagent Organic synthesis Organic compounds Microkinetic models Metal complexes Metal complex Metal carbenes Ligands Ligand Kinetics Hydrogen bond Hydrogen Diazo compounds Dft calculation Density functional theory Decarbonylations Decarbonylation Copper compounds Copper Chemical modification Carbon monoxide Carbon Carbene insertion Carbene Calculation Article
Abstract: Many transition-metal complexes MLn decompose diazo compounds N-2=(CRR2)-R-1 generating metal-carbenes LnM=(CRR2)-R-1 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the (CRR2)-R-1 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 (CRR2)-R-1 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-2=C(H)(CONEt2)], the stable copper carbene Tp(Ms)Cu=C(H)(NEt2) 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)(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.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0002-7863
Author's mail: maria.besora@urv.cat
Author identifier: 0000-0002-6656-5827
Record's date: 2024-07-27
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.1c01483
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 143 (12): 4837-4843
APA: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.; (2021). Two Copper-Carbenes from One Diazo Compound. Journal Of The American Chemical Society, 143(12), 4837-4843. DOI: 10.1021/jacs.1c01483
Article's DOI: 10.1021/jacs.1c01483
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications