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Dicopper Alkyl Complexes: Synthesis, Structure, and Unexpected Persistence
- Source :
- Organometallics. 37:2807-2823
- Publication Year :
- 2018
- Publisher :
- American Chemical Society (ACS), 2018.
-
Abstract
- Cationic μ-alkyl dicopper complexes [Cu2(μ-η1:η1-R)DPFN]NTf2 (R = CH3, CH2CH3, CH2C(CH3)3; DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine NTf2– = N(SO2CF3)2–) were synthesized by treatment of the acetonitrile-bridged dicopper complex [Cu2(μ-η1:η1-NCCH3)DPFN](NTf2)2 with LiR or MgR2. Structural characterization by X-ray crystallography and NMR spectroscopy revealed that the alkyl ligands symmetrically bridge the two copper centers, and the complexes persist in room-temperature solution. Notably, the μ-methyl complex showed less than 20% decomposition after 34 days in room-temperature THF solution. Treatment of the μ-methyl complex with acids allows installation of a range of monoanionic bridging ligands. However, surprisingly insertion into the dicopper–carbon bond was not observed upon addition of a variety of reagents, suggesting that these complexes exhibit a fundamentally new reactivity profile for alkylcopper species. Electrochemical characterization revealed oxidation–reduction events t...
- Subjects :
- chemistry.chemical_classification
010405 organic chemistry
Organic Chemistry
Cationic polymerization
chemistry.chemical_element
Nuclear magnetic resonance spectroscopy
010402 general chemistry
Electrochemistry
01 natural sciences
Medicinal chemistry
Copper
0104 chemical sciences
Inorganic Chemistry
chemistry
Reagent
Physical and Theoretical Chemistry
Alkyl
Subjects
Details
- ISSN :
- 15206041 and 02767333
- Volume :
- 37
- Database :
- OpenAIRE
- Journal :
- Organometallics
- Accession number :
- edsair.doi...........69b84f0c49e3fab7f07bef58224d4ccb