[U(III) {N(SiMe2 tBu)2 }3 ]: a structurally authenticated trigonal planar actinide complex.

[U(III) {N(SiMe2 tBu)2 }3 ]: a structurally authenticated trigonal planar actinide complex.
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DOI:
10.1002/chem.201404864
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发表时间:
2014-11-03
影响因子:
4.3
通讯作者:
Mills, David P.
Mills, David P.
中科院分区:
化学2区
文献类型:
--
作者:
Goodwin, Conrad A. P.;Tuna, Floriana;McInnes, Eric J. L.;Liddle, Stephen T.;McMaster, Jonathan;Vitorica-Yrezabal, Inigo J.;Mills, David P.

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本文报道了铀(III)三酰胺配合物[UIII(N**)3] [1,N**=N(SiMe2tBu)2−]的合成和表征。令人惊讶的是,配合物1在固态下呈现三角平面几何形状,这对于迄今为止仅采用三角金字塔几何形状的三配位锕系元素配合物来说是前所未有的。将[UIII(N**)3]的表征数据与典型的三角锥形铀(III)三酰胺配合物[UIII(N”)3](N”=N(SiMe3)2−)进行了比较,并结合理论计算得出结论,沸石化导致[UIII(N”)3]的净稳定化,但这可以用空间要求非常高的配体,如N** 来克服。1的平面性导致有利的磁动力学,这可以在未来的UIII单分子磁体的设计中考虑。
We report the synthesis and characterization of the uranium(III) triamide complex [UIII(N**)3] [1, N**=N(SiMe2tBu)2−]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three-coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N“)3] (N”=N(SiMe3)2−), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N“)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single-molecule magnets.
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