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• W2888895811 endingPage "11392" @default.
• W2888895811 startingPage "11382" @default.
• W2888895811 abstract "Reaction of the tricopper(I)-dinitrogen tris(β-diketiminate) cyclophane, Cu3(N2)L, with O-atom-transfer reagents or elemental Se affords the oxido-bridged tricopper complex Cu3(μ3-O)L (2) or the corresponding Cu3(μ3-Se)L (4), respectively. For 2 and 4, incorporation of the bridging chalcogen donor was supported by electrospray ionization mass spectrometry and K-edge X-ray absorption spectroscopy (XAS) data. Cu L2,3-edge X-ray absorption data quantify 49.5% Cu 3d character in the lowest unoccupied molecular orbital of 2, with Cu 3d participation decreasing to 33.0% in 4 and 40.8% in the related sulfide cluster Cu3(μ3-S)L (3). Multiedge XAS and UV/visible/near-IR spectra are employed to benchmark density functional theory calculations, which describe the copper-chalcogen interactions as highly covalent across the series of [Cu3(μ-E)]3+ clusters. This result highlights that the metal-ligand covalency is not reserved for more formally oxidized metal centers (i.e., CuIII + O2- vs CuII + O-) but rather is a significant contributor even at more typical ligand-field cases (i.e., Cu3II/II/I + E2-). This bonding is reminiscent of that observed in p-block elements rather than in early-transition-metal complexes." @default.
• W2888895811 created "2018-09-07" @default.
• W2888895811 creator A5002953655 @default.
• W2888895811 creator A5006857139 @default.
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• W2888895811 creator A5035546110 @default.
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• W2888895811 creator A5066934639 @default.
• W2888895811 creator A5072472177 @default.
• W2888895811 creator A5091491667 @default.
• W2888895811 date "2018-08-30" @default.
• W2888895811 modified "2023-10-18" @default.
• W2888895811 title "Chalcogen Impact on Covalency within Molecular [Cu₃(μ₃-E)]³⁺ Clusters (E = O, S, Se): A Synthetic, Spectroscopic, and Computational Study" @default.
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• W2888895811 doi "https://doi.org/10.1021/acs.inorgchem.8b01000" @default.

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