Volume 19, Issue 31 p. 10287-10294
Full Paper

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

Guy M. Jones

Guy M. Jones

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

Prof. Polly L. Arnold

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) 131-6504743Search for more papers by this author
Dr. Jason B. Love

Corresponding Author

Dr. Jason B. Love

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) 131-6504743Search for more papers by this author
First published: 21 June 2013
Citations: 38

Graphical Abstract

Keeping it in the carbon family: Simple and versatile metalation and exchange reactions lead to a new family of binuclear uranium(V)–oxo complexes that are functionalised by the Group 14 elements C, Si, and Sn. These Pacman-shaped compounds display distinct UO single and multiple bonding patterns and exhibit unique stability against oxidation (see scheme).

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 UO 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-OC 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.