Sarsfield Mark J, Helliwell Madeleine
Centre for Radiochemistry Research, Department of Chemistry, The University of Manchester, Manchester, M13 9PL United Kingdom.
J Am Chem Soc. 2004 Feb 4;126(4):1036-7. doi: 10.1021/ja039101y.
Treatment of the thf adduct UO2(NCN)thf (NCN = [(Me3SiN)CPh(NSiMe3)]) (1) with 2 equiv of B(C6F5)3 provides UO{OB(C6F5)3}(NCN)2 (2) the first example of a neutral uranyl complex exhibiting Lewis basic behavior. The crystal structure of 2 shows a U=O-B interaction with an elongated U=O bond (1.898(3) A). Raman spectroscopy suggests weakening of the O=U=O bonding, giving the lowest reported symmetric stretching frequency for a monomeric uranyl complex, nu1 = 780 cm-1. The borane can be selectively removed using PMe3 to give the coordinatively unsaturated UO2(NCN)2 (3) or using tBuNC to provide UO2(CNBut)(NCN)2 (4), the first example of an isonitrile coordinated to uranium.
用2当量的B(C6F5)3处理四氢呋喃加合物UO2(NCN)thf（NCN = [(Me3SiN)CPh(NSiMe3)]）（1），得到UO{OB(C6F5)3}(NCN)2（2），这是首例表现出路易斯碱行为的中性铀酰配合物。2的晶体结构显示出U=O-B相互作用以及伸长的U=O键（1.898(3) Å）。拉曼光谱表明O=U=O键减弱，给出了单体铀酰配合物中报道的最低对称伸缩频率，ν1 = 780 cm-1。可以使用PMe3选择性地除去硼烷，得到配位不饱和的UO2(NCN)2（3），或者使用tBuNC得到UO2(CNBut)(NCN)2（4），这是异腈与铀配位的首例。
