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Oxo–Group-14-Element Bond Formation in Binuclear Uranium(V) Pacman Complexes

Authors

  • Guy M. Jones,

    1. EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ (U.K.), Fax: (+44) 131-6504743
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  • Prof. Polly L. Arnold,

    Corresponding author
    1. EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ (U.K.), Fax: (+44) 131-6504743
    • EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ (U.K.), Fax: (+44) 131-6504743

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  • Dr. Jason B. Love

    Corresponding author
    1. EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ (U.K.), Fax: (+44) 131-6504743
    • EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ (U.K.), Fax: (+44) 131-6504743

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Abstract

Simple and versatile routes to the functionalization of uranyl-derived UV–oxo groups are presented. The oxo-lithiated, binuclear uranium(V)–oxo complexes [{(py)3LiOUO}2(L)] and [{(py)3LiOUO}(OUOSiMe3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide “ate” complex [Li(py)2][(OUO)(N”)3] (N”=N(SiMe3)2) with the polypyrrolic macrocycle H4L or the mononuclear uranyl (VI) Pacman complex [UO2(py)(H2L)], respectively. These oxo-metalated complexes display distinct U[BOND]O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo–stannylated complexes [{(R3Sn)OUO}2(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium–oxo-group exchange occurred in reactions with [TiCl(OiPr)3] to form U-O[BOND]C bonds [{(py)3LiOUO}(OUOiPr)(L)] and [(iPrOUO)2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements.

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