由四（异丙基）环戊二烯基配体支撑的三价和四价铀金属茂的异腈加合物。

Isocyanide adducts of tri- and tetravalent uranium metallocenes supported by tetra(isopropyl)cyclopentadienyl ligands.

作者信息

Boreen Michael A, Groß Oliver A, Hohloch Stephan, Arnold John

机构信息

Department of Chemistry, University of California, Berkeley, California 94720, USA.

Paderborn University, Warburger Straße 100, 33098 Paderborn, Germany.

出版信息

Dalton Trans. 2020 Sep 1;49(34):11971-11977. doi: 10.1039/d0dt02005b.

DOI:10.1039/d0dt02005b

PMID:32812574

Abstract

Reaction of the uranium(iii) metallocenium salt [(CpiPr4)2U][B(C6F5)4] with tert-butyl isocyanide (tBuNC) yielded the dicationic uranium(iv) complex [(CpiPr4)2U(CNtBu)4][B(C6F5)4]2 (1), which displays a linear metallocene geometry. Use of crude mixtures of [(CpiPr4)2U][B(C6F5)4], which contain a soluble source of iodide, led instead to isolation of the monocationic uranium(iv) iodide complex [(CpiPr4)2U(I)(CNtBu)2][B(C6F5)4] (2). Adduct formation with no change in oxidation state was observed upon addition of tBuNC to the neutral uranium(iii) species (CpiPr4)2UI, resulting in isolation of (CpiPr4)2U(I)(CNtBu) (3). X-ray crystallographic and IR spectroscopic studies both showed effects ascribed to the presence of multiple strongly donating isocyanide ligands in 1.

摘要

铀（III）茂金属盐[(CpiPr4)2U][B(C6F5)4]与叔丁基异腈（tBuNC）反应生成了二价铀（IV）配合物[(CpiPr4)2U(CNtBu)4][B(C6F5)4]2（1），其呈现出线性茂金属几何结构。使用含有可溶性碘源的[(CpiPr4)2U][B(C6F5)4]粗混合物，反而得到了单价铀（IV）碘配合物[(CpiPr4)2U(I)(CNtBu)2][B(C6F5)4]（2）。向中性铀（III）物种（CpiPr4)2UI中加入tBuNC时，观察到形成了加合物且氧化态不变，从而得到了（CpiPr4)2U(I)(CNtBu)（3）。X射线晶体学和红外光谱研究均表明，1中多个强给电子异腈配体的存在产生了影响。