New options in directed cupration: Studies in heteroleptic bis(amido)cuprate formation Dedicated to the memory of Jack Lewis.
Journal of Organometallic Chemistry
MetadataShow full item record
Peel, A., Slaughter, J., & Wheatley, A. (2016). New options in directed cupration: Studies in heteroleptic bis(amido)cuprate formation Dedicated to the memory of Jack Lewis.. Journal of Organometallic Chemistry, 812 259-267. https://doi.org/10.1016/j.jorganchem.2015.09.038
The 2:1 combination of MPLi (MP = 2-methylpiperidide) with CuBr gives the novel complex [(MP)₂CuLi(THF)₂]₂LiBr 12 and introduces the chiral ligand MP to the evolving field of directed ortho cupration reagents. Subsequent syntheses have focused on developing heteroleptic bis(amido) arrangements at Cu, with 1:1 mixtures of two out of MPLi, DMPLi and TMPLi (DMP = 2,6-cis-dimethylpiperidide; TMP = 2,2,6,6-tetramethylpiperidide) being reacted with CuI salts in the presence of THF. Resulting lithiocuprates reveal solid state dimers based on the heteroleptic bis(amido) formulations R₂N(TMP)Cu(Br)Li₂(THF)₂ (R₂N = MP 13; AM = DMP 14). The heteroleptic Gilman lithiocuprate PIP(TMP)CuLi (PIP = piperidide) 15 has also been prepared. In each of 12-15, significant variations in the orientations of the amide ligands can be rationalized in terms of steric effects and, in the case of 15, stabilization of the alkali metal by Me---Li interaction is evidenced.
Amide ligand, Cuprate, Lithium, Structure, X-ray crystallography
This work was supported by the U.K. EPSRC through grant EP/J500380/1 (A.P.).
External DOI: https://doi.org/10.1016/j.jorganchem.2015.09.038
This record's URL: https://www.repository.cam.ac.uk/handle/1810/251231
Attribution 4.0 International
Licence URL: http://creativecommons.org/licenses/by/4.0/