Dicopper(I,I) and delocalized mixed-valent dicopper(I,II) complexes of a sterically hindered carboxylate ligand

John R. Hagadorn; Theresa I. Zahn; Lawrence Que; William B. Tolman

doi:10.1039/b301154b

Dicopper(I,I) and delocalized mixed-valent dicopper(I,II) complexes of a sterically hindered carboxylate ligand

John R. Hagadorn, Theresa I. Zahn, Lawrence Que, William B. Tolman

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

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Abstract

Admixture of the lithium salt of the bulky ligand 2,6-dimesitylbenzoate [ArCO₂]^- with [Cu(CH₃CN)₄]O ₃SCF₃ yielded the dicopper(I,I) complex [(ArCO ₂)₂Cu₂(THF)₂)] (1), which upon oxidation with AgX (X = SbF₆^- or ClO₄ ^-) in THF afforded the mixed-valent complexes [(ArCO ₂)₂Cu₂(THF)₂]SbF₆ (2) and [(ArCO₂)₂Cu₂(THF)₃]ClO₄ (3), respectively. Fully delocalized mixed-valent (Cu^1.5Cu ^1.5) formulations for 2 and 3 were determined on the basis of X-ray crystallography and UV-vis, resonance Raman, ¹H 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.

Original language	English (US)
Pages (from-to)	1790-1794
Number of pages	5
Journal	Dalton Transactions
Issue number	9
DOIs	https://doi.org/10.1039/b301154b
State	Published - May 7 2003

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title = "Dicopper(I,I) and delocalized mixed-valent dicopper(I,II) complexes of a sterically hindered carboxylate ligand",

abstract = "Admixture of the lithium salt of the bulky ligand 2,6-dimesitylbenzoate [ArCO2]- with [Cu(CH3CN)4]O 3SCF3 yielded the dicopper(I,I) complex [(ArCO 2)2Cu2(THF)2)] (1), which upon oxidation with AgX (X = SbF6- or ClO4 -) in THF afforded the mixed-valent complexes [(ArCO 2)2Cu2(THF)2]SbF6 (2) and [(ArCO2)2Cu2(THF)3]ClO4 (3), respectively. Fully delocalized mixed-valent (Cu1.5Cu 1.5) formulations for 2 and 3 were determined on the basis of X-ray crystallography and UV-vis, resonance Raman, 1H 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.",

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T1 - Dicopper(I,I) and delocalized mixed-valent dicopper(I,II) complexes of a sterically hindered carboxylate ligand

AU - Hagadorn, John R.

AU - Zahn, Theresa I.

AU - Que, Lawrence

AU - Tolman, William B.

PY - 2003/5/7

Y1 - 2003/5/7

N2 - Admixture of the lithium salt of the bulky ligand 2,6-dimesitylbenzoate [ArCO2]- with [Cu(CH3CN)4]O 3SCF3 yielded the dicopper(I,I) complex [(ArCO 2)2Cu2(THF)2)] (1), which upon oxidation with AgX (X = SbF6- or ClO4 -) in THF afforded the mixed-valent complexes [(ArCO 2)2Cu2(THF)2]SbF6 (2) and [(ArCO2)2Cu2(THF)3]ClO4 (3), respectively. Fully delocalized mixed-valent (Cu1.5Cu 1.5) formulations for 2 and 3 were determined on the basis of X-ray crystallography and UV-vis, resonance Raman, 1H 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.

AB - Admixture of the lithium salt of the bulky ligand 2,6-dimesitylbenzoate [ArCO2]- with [Cu(CH3CN)4]O 3SCF3 yielded the dicopper(I,I) complex [(ArCO 2)2Cu2(THF)2)] (1), which upon oxidation with AgX (X = SbF6- or ClO4 -) in THF afforded the mixed-valent complexes [(ArCO 2)2Cu2(THF)2]SbF6 (2) and [(ArCO2)2Cu2(THF)3]ClO4 (3), respectively. Fully delocalized mixed-valent (Cu1.5Cu 1.5) formulations for 2 and 3 were determined on the basis of X-ray crystallography and UV-vis, resonance Raman, 1H 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.

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JF - Dalton Transactions

IS - 9

ER -

Dicopper(I,I) and delocalized mixed-valent dicopper(I,II) complexes of a sterically hindered carboxylate ligand

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