Dicopper Alkyl Complexes: Synthesis, Structure, and
Unexpected Persistence
Version 2 2018-08-10, 11:19
Version 1 2018-08-08, 18:48
Posted on 2018-08-10 - 11:19
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 that evidence putative mixed-valence dicopper alkyl complexes.
Computational studies suggest that the dicopper–carbon bonds
are highly covalent, possibly explaining their remarkable stability.
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Ziegler, Micah S.; Torquato, Nicole A.; Levine, Daniel S.; Nicolay, Amélie; Celik, Hasan; Tilley, T. Don (2018). Dicopper Alkyl Complexes: Synthesis, Structure, and
Unexpected Persistence. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.8b00443
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AUTHORS (6)
MZ
Micah S. Ziegler
NT
Nicole A. Torquato
DL
Daniel S. Levine
AN
Amélie Nicolay
HC
Hasan Celik
TT
T. Don Tilley