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- W4385580710 abstract "Understanding the electronic structures of high-valent metal complexes aids the advancement of metal-catalyzed cross coupling methodologies. A prototypical complex with formally high valency is [Cu(CF3)4]- (1), which has a formal Cu(III) oxidation state but whose physical analysis has led some to a Cu(I) assignment in an inverted ligand field model. Recent ex- aminations of 1 by X-ray spectroscopies have led to contradictory conclusions, motivating the re-examining of its X-ray ab- sorption profile here by a complementary method, resonant diffraction anomalous fine structure (DAFS). From analysis of DAFS measurements for a series of seven mononuclear Cu complexes including 1, here it is shown that there is a systematic trifluoromethyl effect on X-ray absorption that blue shifts the resonant Cu K-edge energy by 2-3 eV per CF3, completely ac- counting for observed changes in DAFS profiles between formally Cu(III) complexes like 1 and formally Cu(I) complexes like (Ph3P)3CuCF3 (3). Thus, in agreement with the inverted ligand field model, the data presented herein imply that 1 is best described as containing a Cu(I) ion with d10 configuration." @default.
- W4385580710 created "2023-08-05" @default.
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- W4385580710 date "2023-08-04" @default.
- W4385580710 modified "2023-09-27" @default.
- W4385580710 title "Uncovering a CF3 effect on X-ray absorption energies of [Cu(CF3)4]- and related Cu compounds with inverted ligand fields using resonant diffraction anomalous fine structure (DAFS) measurements" @default.
- W4385580710 doi "https://doi.org/10.26434/chemrxiv-2023-klcfp" @default.
- W4385580710 hasPublicationYear "2023" @default.
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