一个硫和铀的狂欢节！中性端铀(VI)单硫化物、铀(VI)η-二硫化物和铀(IV)膦硫化物配合物的合成、结构和特性。

A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium(vi) monosulphide, uranium(vi) η-disulphide, and uranium(iv) phosphine sulphide complexes.

机构信息

Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA.

出版信息

Dalton Trans. 2018 Dec 18;48(1):50-57. doi: 10.1039/c8dt02932f.

Abstract

Three new uranium species (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S), (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2), and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) were synthesized and fully characterized by a combination of NMR, IR, and UV/vis-NIR spectroscopies, elemental analysis, and cyclic voltammetry. The solid state structures of (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(η2-S2) were also determined. The compound (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) is the first neutral uranium complex with a terminal sulphido ligand, and (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3) is the first uranium compound with a coordinated phosphine sulphide ligand. The phosphine sulphide adduct, (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(S[double bond, length as m-dash]PMe3), can be synthesized either by reaction of the uranium(iv) complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)(thf) with S[double bond, length as m-dash]PMe3 or by the reaction of the uranium(vi) terminal sulphido complex (C5Me5)2U([double bond, length as m-dash]N-2,6-iPr2-C6H3)([double bond, length as m-dash]S) with PMe3.

摘要

三种新的铀物种（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)([双键，长度为破折号]S)、（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(η2-S2)和（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(S[双键，长度为破折号]PMe3)通过 NMR、IR 和 UV/vis-NIR 光谱、元素分析和循环伏安法的组合进行了合成和全面表征。（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)([双键，长度为破折号]S)和（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(η2-S2)的固态结构也得到了确定。化合物（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)([双键，长度为破折号]S)是第一个具有末端硫代配体的中性铀配合物，（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(S[双键，长度为破折号]PMe3)是第一个具有配位膦硫代配体的铀化合物。磷硫代加合物（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(S[双键，长度为破折号]PMe3)可以通过反应铀(iv)配合物（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)(thf)与 S[双键，长度为破折号]PMe3 或通过反应铀(vi)末端硫代配合物（C5Me5）2U([双键，长度为破折号]N-2,6-iPr2-C6H3)([双键，长度为破折号]S)与 PMe3 合成。