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• W1965572555 endingPage "11891" @default.
• W1965572555 startingPage "11879" @default.
• W1965572555 abstract "A series of organometallic pentavalent uranium complexes of the general formula (C5Me5)2U(=N-2,6-iPr2-C6H3)(Y) (Y = monoanionic, non-halide ligand) have been prepared using a variety of routes. Utilizing the direct oxidation of (C5Me5)2U(=N-2,6-iPr2-C6H3)(THF) (2) with the appropriate copper(I) salt yielded the triflate (Y = OTf (OSO2CF3), 11), thiolate (Y = SPh, 12), and acetylide (Y = C≡CPh, 13) complexes, while a salt metathesis route between the UV-imido (C5Me5)2U(=N-2,6-iPr2-C6H3)(I) (10) and various alkali salts gave the diphenylamide (Y = NPh2, 14), aryloxide (Y = OPh, 15), alkyl (Y = Me, 16), and aryl (Y = Ph, 17) complexes. Paired with 13, the isolation of 16 and 17 shows that UV can support the full range of carbon anions (sp, sp2, and sp3), and these are, to the best of our knowledge, the first examples of pentavalent uranium complexes with anionic carbon moieties other than carbocyclic (C5R5, C7H7, C8H8) ligands. Finally, both protonolysis and insertion pathways afforded the UV-imido ketimide complex (C5Me5)2U(=N-2,6-iPr2-C6H3)(N=CPh2) (18). The complexes have been isolated in good yield and characterized using various combinations of 1H NMR spectroscopy, elemental analysis, mass spectrometry, single crystal X-ray diffraction, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and magnetic susceptibility measurements. All (C5Me5)2U(=N−Ar)(X) (X = F, Cl, Br, I) and (C5Me5)2U(=N−Ar)(Y) complexes exhibit UVI/UV and UV/UIV redox couples by voltammetry. The potential separation between these couples remains essentially constant at ∼1.50 V, but both processes shift in tandem in potential by ∼700 mV across the series of X/Y ligands. No significant differences between μeff values or temperature dependencies in the magnetic susceptibility were observed for these complexes regardless of the identity of the ancillary X/Y ligand. However, an excellent linear correlation was observed between the chemical shift values of C5Me5 ligand protons in the 1H NMR spectra and the oxidation potentials of (C5Me5)2U(=N-2,6-iPr2-C6H3)(X/Y), suggesting that there is a common origin, overall σ-/π-donation from the ancillary X/Y ligand to the metal, contributing to both observables. Combined, these data confer the following trend in increasing σ/π-donating ability of the X/Y ligand to the UV metal center: OTf < I < Br < Cl < SPh < C≡CPh < F < [OPh ∼ Me ∼ Ph] ≪ NPh2 < N=CPh2. These (C5Me5)2U(=N-2,6-iPr2-C6H3)(X/Y) complexes also show distinct hallmarks of a covalent bonding interaction between the metal and the imide ligand that is modulated to varying degrees by the interaction between the X/Y ancillary ligand and the UV metal center. These signatures of covalency include stabilization of multiple metal oxidations states [UVI, UV, and UIV] and enhanced intensities in the intraconfiguration (f-f) transitions. Of particular note in this regard is the more than 20-fold enhancement in the f-f intensities observed for Y = C≡CPh and N=CPh2, which is a clear reflection of the covalent metal-ligand bonding interactions sustained by the acetylide and ketimide ligands in these pentavalent systems." @default.
• W1965572555 created "2016-06-24" @default.
• W1965572555 creator A5030873133 @default.
• W1965572555 creator A5033721117 @default.
• W1965572555 creator A5055551254 @default.
• W1965572555 creator A5060165563 @default.
• W1965572555 creator A5067137772 @default.
• W1965572555 creator A5080035090 @default.
• W1965572555 creator A5086837942 @default.
• W1965572555 date "2008-11-18" @default.
• W1965572555 modified "2023-10-18" @default.
• W1965572555 title "Probing the Chemistry, Electronic Structure and Redox Energetics in Organometallic Pentavalent Uranium Complexes" @default.
• W1965572555 cites W1547130499 @default.
• W1965572555 cites W1595392362 @default.
• W1965572555 cites W1964160141 @default.
• W1965572555 cites W1964640330 @default.
• W1965572555 cites W1965654005 @default.
• W1965572555 cites W1968477216 @default.
• W1965572555 cites W1970951785 @default.
• W1965572555 cites W1971038878 @default.
• W1965572555 cites W1971451395 @default.
• W1965572555 cites W1976169026 @default.
• W1965572555 cites W1977669449 @default.
• W1965572555 cites W1984178497 @default.
• W1965572555 cites W1985515513 @default.
• W1965572555 cites W1987343831 @default.
• W1965572555 cites W1988072290 @default.
• W1965572555 cites W1988901166 @default.
• W1965572555 cites W1989250325 @default.
• W1965572555 cites W1989852103 @default.
• W1965572555 cites W1990143606 @default.
• W1965572555 cites W1991785854 @default.
• W1965572555 cites W1993561241 @default.
• W1965572555 cites W1993628226 @default.
• W1965572555 cites W1993950774 @default.
• W1965572555 cites W1998121578 @default.
• W1965572555 cites W1998731725 @default.
• W1965572555 cites W1998937082 @default.
• W1965572555 cites W1999670950 @default.
• W1965572555 cites W2003063429 @default.
• W1965572555 cites W2005252890 @default.
• W1965572555 cites W2009596744 @default.
• W1965572555 cites W2009656057 @default.
• W1965572555 cites W2010038649 @default.
• W1965572555 cites W2010866284 @default.
• W1965572555 cites W2012782567 @default.
• W1965572555 cites W2013850403 @default.
• W1965572555 cites W2016756692 @default.
• W1965572555 cites W2016913560 @default.
• W1965572555 cites W2020007000 @default.
• W1965572555 cites W2020279342 @default.
• W1965572555 cites W2021674019 @default.
• W1965572555 cites W2021963685 @default.
• W1965572555 cites W2022695096 @default.
• W1965572555 cites W2026925925 @default.
• W1965572555 cites W2030478969 @default.
• W1965572555 cites W2033253310 @default.
• W1965572555 cites W2034574511 @default.
• W1965572555 cites W2036052815 @default.
• W1965572555 cites W2037324324 @default.
• W1965572555 cites W2040338073 @default.
• W1965572555 cites W2040573684 @default.
• W1965572555 cites W2043800343 @default.
• W1965572555 cites W2044956834 @default.
• W1965572555 cites W2045247507 @default.
• W1965572555 cites W2046522513 @default.
• W1965572555 cites W2050265796 @default.
• W1965572555 cites W2051058309 @default.
• W1965572555 cites W2052462331 @default.
• W1965572555 cites W2055038447 @default.
• W1965572555 cites W2056388446 @default.
• W1965572555 cites W2059960675 @default.
• W1965572555 cites W2059982398 @default.
• W1965572555 cites W2063074480 @default.
• W1965572555 cites W2063673531 @default.
• W1965572555 cites W2069266641 @default.
• W1965572555 cites W2069767745 @default.
• W1965572555 cites W2076546523 @default.
• W1965572555 cites W2077215934 @default.
• W1965572555 cites W2082024019 @default.
• W1965572555 cites W2083518550 @default.
• W1965572555 cites W2084509454 @default.
• W1965572555 cites W2085055453 @default.
• W1965572555 cites W2085353582 @default.
• W1965572555 cites W2086628779 @default.
• W1965572555 cites W2095583759 @default.
• W1965572555 cites W2097720788 @default.
• W1965572555 cites W2105689911 @default.
• W1965572555 cites W2168915189 @default.
• W1965572555 cites W2322573838 @default.
• W1965572555 cites W274377105 @default.
• W1965572555 cites W2885920431 @default.
• W1965572555 cites W290602997 @default.
• W1965572555 cites W2951244216 @default.
• W1965572555 cites W3004598420 @default.
• W1965572555 cites W4239223884 @default.
• W1965572555 cites W2089746584 @default.
• W1965572555 doi "https://doi.org/10.1021/ic8017375" @default.

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