EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh, EH9 3 JJ, UK.
Chemistry. 2013 Jul 29;19(31):10287-94. doi: 10.1002/chem.201301067. Epub 2013 Jun 21.
Simple and versatile routes to the functionalization of uranyl-derived U(V)-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-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-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.
介绍了几种将铀酰衍生的 U(V)-氧基团功能化的简单而通用的方法。通过直接组合铀(VI)硅酰胺“ate”配合物[Li(py)2](OUO)(N")3与多吡咯大环 H4L 或单核铀(VI)Pacman 配合物[UO2(py)(H2L)]，制备了氧锂化的双核铀(V)-氧配合物[{(py)3LiOUO}2(L)]和[{(py)3LiOUO}(OUOSiMe3)(L)]。这些氧金属化配合物显示出不同的 U-O 单键和多重键合模式以及氧配体的轴向/赤道排列。它们的易得性允许直接对铀氧基进行功能化，得到双核铀(V)氧锡化配合物{(R3Sn)OUO}2(L)，它们代表了混合铀/锡配合物的罕见实例。此外，与[TiCl(OiPr)3]的反应发生了铀-氧基团交换，形成了 U-O-C 键[{(py)3LiOUO}(OUOiPr)(L)]和[(iPrOUO)2(L)]。总的来说，这些是第一组通过第 14 族元素对铀(V)配合物进行氧功能化的配合物。
