Abstract
Admixture of the lithium salt of the bulky ligand 2,6-dimesitylbenzoate [ArCO
2
]
−
with [Cu(CH
3
CN)
4
]O
3
SCF
3
yielded the dicopper(
i
,
i
) complex [(ArCO
2
)
2
Cu
2
(THF)
2
)] (
1
), which upon oxidation with AgX (X = SbF
6
−
or ClO
4
−
) in THF afforded the mixed-valent complexes [(ArCO
2
)
2
Cu
2
(THF)
2
]SbF
6
(
2
) and [(ArCO
2
)
2
Cu
2
(THF)
3
]ClO
4
(
3
), respectively. Fully delocalized mixed-valent (Cu
1.5
Cu
1.5
) formulations for
2
and
3
were determined on the basis of X-ray crystallography and UV-vis, resonance Raman,
1
H NMR, and EPR spectroscopy. Notably, solvent dependent UV-vis spectra suggest that THF and or counter ion coordination influence the intermetal bonding interactions in the mixed-valent cores.
Solvent dependent UV-vis spectra suggest that THF and or counter ion coordination influence the inter-metal bonding interactions in the mixed valence cores of dicopper(
i
,
ii
) complexes supported by bulky carboxylates.