Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis-Dioxo Fleeting Intermediate

被引:8
|
作者
Hartline, Douglas R. [1 ]
Loeftier, Sascha T. [1 ]
Fehn, Dominik [1 ]
Kasper, Joseph M. [2 ]
Heinemann, Frank W. [1 ]
Yang, Ping [2 ]
Batista, Enrique R. [2 ]
Meyer, Karsten [1 ]
机构
[1] Friedrich Alexander Univ Erlangen Nurnberg FAU, Dept Chem & Pharm, Inorgan Chem, D-91058 Erlangen, Germany
[2] Los Alamos Natl Lab, Theoret Div, Los Alamos, NM 87545 USA
关键词
PHOTOCHEMICAL-SYNTHESIS; OXIDATIVE ADDITION; COMPLEXES; URANYL; CHEMISTRY; CRYSTAL; U(IV); SE; ELIMINATION; THORIUM;
D O I
10.1021/jacs.2c12868
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The activation of chalcogen-chalcogen bonds using organometallic uranium complexes has been well documented for S-S, Se-Se, and Te-Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O-O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O-O bond cleavage of 9,10-diphenylanthracene-9,10endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [((Me,AdArO)3N)UIII(dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [((Me,AdArO)3N)UV(DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. This uranium(V) bis-alkoxide can then be reduced with KC8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.
引用
收藏
页码:8927 / 8938
页数:12
相关论文
共 7 条
  • [1] Uranium-mediated activation of small molecules
    Arnold, Polly L.
    CHEMICAL COMMUNICATIONS, 2011, 47 (32) : 9005 - 9010
  • [2] Uranium-mediated carbon dioxide activation and functionalization
    Meyer, Karsten
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2012, 243
  • [3] Uranium-mediated carbon dioxide activation and functionalization
    Lam, Oanh P.
    Meyer, Karsten
    POLYHEDRON, 2012, 32 (01) : 1 - 9
  • [4] Multimetallic Cooperativity in Uranium-Mediated CO2 Activation
    Cooper, Oliver
    Camp, Clement
    Pecaut, Jacques
    Kefalidis, Christos E.
    Maron, Laurent
    Gambarelli, Serge
    Mazzanti, Marinella
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (18) : 6716 - 6723
  • [5] Multimetallic cooperativity in uranium-mediated CO2 activation
    20142017731544
    Mazzanti, M. (marinella.mazzanti@cea.fr), 1600, American Chemical Society (136):
  • [6] Thorium- and Uranium-Mediated C-H Activation of a Silyl-Substituted Cyclobutadienyl Ligand
    Tsoureas, Nikolaos
    Rajeshkumar, Thayalan
    Townrow, Oliver P. E.
    Maron, Laurent
    Layfield, Richard A.
    INORGANIC CHEMISTRY, 2022, 61 (50) : 20629 - 20635
  • [7] Spectroscopic and Theoretical Insights into H2 Activation on Uranium Monoxide: Homolytic H2 Cleavage Mediated by Intermediate OU(η2-H2)
    Pu, Zhen
    Fu, Xiaoguo
    Qin, Jianwei
    Yang, Hu
    Shuai, Maobing
    Li, Fang
    INORGANIC CHEMISTRY, 2024, 63 (29) : 13304 - 13310