Oxo-group-14-element bond formation in binuclear uranium(V) Pacman complexes.
Oxo-group-14-element bond formation in binuclear uranium(V) Pacman complexes.
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DOI：
10.1002/chem.201301067
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发表时间：
2013-07
期刊：
影响因子：
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通讯作者：
Guy M. Jones;P. Arnold;J. Love
中科院分区：
文献类型：
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作者：
Guy M. Jones;P. Arnold;J. Love
介绍了铀酰衍生的U（V）-氧代基团的功能化的简单和通用的路线。通过将铀酰硅酰胺配合物[Li（py）2][（OUO）（N”）3]（N”= N（SiMe 3）2）分别与聚吡咯大环H4 L或单核铀酰Pacman配合物[UO 2（py）（H2 L）]直接结合，制备了氧代锂化双核铀（V）-氧代配合物[{（py）3LiOUO}2（L）]和[{（py）3LiOUO}（OUO SiMe 3）（L）].这些氧代金属配合物显示不同的U-O单键和多键模式和轴向/赤道排列的氧代配体。它们的易得性允许直接官能化铀酰氧代基团，导致双核铀（V）氧代锡酰化配合物[{（R3 Sn）OUO}2（L）]（R = nBu，Ph），其代表混合铀/锡配合物的罕见实例。此外，在与[TiCl（OiPr）3]的反应中发生铀-氧代-基团交换以形成U-O-C键[{（py）3LiOUO}（OUOiPr）（L）]和[（iPrOUO）2（L）]。总的来说，这些代表了第一个由第14族元素氧代官能化的铀（V）络合物家族。
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.