Probing the reactivity and electronic structure of a uranium(V) terminal oxo complex.
作者： Skye Fortier , Nikolas Kaltsoyannis , Guang Wu , Trevor W. Hayton
DOI: 10.1021/JA206083P
关键词: Photochemistry 、 Metallacycle 、 Chemistry 、 Reactivity (chemistry) 、 Electronic structure 、 Adduct 、 Nucleophile 、 Yield (chemistry) 、 Medicinal chemistry 、 Uranium
摘要: Treatment of the U(III)–ylide adduct U(CH2PPh3)(NR2)3 (1, R = SiMe3) with TEMPO generates U(V) oxo metallacycle [Ph3PCH3][U(O)(CH2SiMe2NSiMe3)(NR2)2] (2) via O-atom transfer, in good yield. Oxidation 2 0.85 equiv AgOTf affords neutral U(VI) species U(O)(CH2SiMe2NSiMe3)(NR2)2 (3). The electronic structures and 3 are investigated by DFT analysis. Additionally, nucleophilicity ligands toward Me3SiI is explored.
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Mark J. Sarsfield, Helen Steele, Madeleine Helliwell, Simon J. Teat, Uranyl bis-iminophosphorane complexes with in- and out-of-plane equatorial coordinationElectronic supplementary information (ESI) available: Variable temperature 1H NMR spectra; Raman spectra; solid state diffuse reflectance electronic absorption spectra; luminescence spectra; interatomic distances of the optimised structures of 1* and 2* from molecular modelling calculations. See http://www.rsc.org/suppdata/dt/b3/b304602h/ Dalton Transactions. pp. 3443- 3449 ,(2003) , 10.1039/B304602H
Skye Fortier, Guang Wu, Trevor W. Hayton, Synthesis of a Nitrido-Substituted Analogue of the Uranyl Ion, [N═U═O]+ Journal of the American Chemical Society. ,vol. 132, pp. 6888- 6889 ,(2010) , 10.1021/JA101567H
Guofu Zi, Li Jia, Evan L. Werkema, Marc D. Walter, Jochen P. Gottfriedsen, Richard A. Andersen, Preparation and Reactions of Base-Free Bis(1,2,4-tri-tert-butylcyclopentadienyl)uranium Oxide, Cp‘2UO Organometallics. ,vol. 24, pp. 4251- 4264 ,(2005) , 10.1021/OM050406Q
Carol J. Burns, Wayne H. Smith, John C. Huffman, Alfred P. Sattelberger, Uranium(VI) organoimido complexes Journal of the American Chemical Society. ,vol. 112, pp. 3237- 3239 ,(1990) , 10.1021/JA00164A069
Aaron L. Odom, Daniel J. Mindiola, Christopher C. Cummins, A Nucleophilic Chromium(V) Dioxo Radical Anion. Inorganic Chemistry. ,vol. 38, pp. 3290- 3295 ,(1999) , 10.1021/IC981403R
Emma O'Grady, Nikolas Kaltsoyannis, On the inverse trans influence. Density functional studies of [MOX5]n− (M = Pa, n= 2; M = U, n= 1; M = Np, n= 0; X = F, Cl or Br) Journal of The Chemical Society-dalton Transactions. pp. 1233- 1239 ,(2002) , 10.1039/B109696F
Cameron A. Lippert, Jake D. Soper, Deoxygenation of nitroxyl radicals by oxorhenium(V) complexes with redox-active ligands. Inorganic Chemistry. ,vol. 49, pp. 3682- 3684 ,(2010) , 10.1021/IC9024684
David S. J. Arney, Carol J. Burns, Synthesis and structure of high-valent organouranium complexes containing terminal monooxo functional groups Journal of the American Chemical Society. ,vol. 115, pp. 9840- 9841 ,(1993) , 10.1021/JA00074A077
Ahmet Gunay, Klaus H. Theopold, C-H bond activations by metal oxo compounds. Chemical Reviews. ,vol. 110, pp. 1060- 1081 ,(2010) , 10.1021/CR900269X
Suzanne C. Bart, Christian Anthon, Frank W. Heinemann, Eckhard Bill, Norman M. Edelstein, Karsten Meyer, Carbon dioxide activation with sterically pressured mid- and high-valent uranium complexes. Journal of the American Chemical Society. ,vol. 130, pp. 12536- 12546 ,(2008) , 10.1021/JA804263W