REDUCTION OF ORGANOMETALLIC URANIUM (IV) BY MEANS OF CONTROLLED-POTENTIAL ELECTROLYSIS.

一个紧凑的不锈钢手套箱已经准备好。主腔和侧腔可以独立抽真空，然后充入惰性气体。主腔室有循环冷却水的进口和出口。由于主室中的压差经常随着有机材料的使用而改变，并且为了装载在真空中不受抵抗的东西，惰性气体可以连续地通过两个室。在主室中准备好用于处理二聚化合物和电化学研究的装置。二聚双环戊二烯被解聚，所得的环戊二烯被储存在冷冻箱中，以防止在使用前再聚合。在配备有回流冷凝器和用于氩气鼓泡的毛细管的三颈烧瓶中，放置乙醚和钾金属片，并加入有限量的环戊二烯。蒸发溶剂后，将钾络合物浓缩。 ...更多信息 过滤并洗涤通过加入过氧化氢从硝酸铀酰溶液中沉淀的过氧化铀，并通过在空气中在400 ℃下加热将其转化为无定形氧化铀（VI）。过滤并洗涤通过无定形氧化铀（VI）与六氯丙烯反应制备的氯化铀（IV），并将其用于在四氢呋喃中与环戊二烯基钾反应制备四环戊二烯基铀（IV）。通过用正戊烷萃取除去过量的钾络合物。用循环伏安法研究了铀在含四环戊二烯基铀（IV）有机溶剂中的氧化还原反应。铂丝用作工作电极和对电极，银丝用作参比电极。记录的铀（III）/铀（IV）电对的循环伏安图显示了氧化还原电对的可逆性，并获得了有关铀（IV）/铀（V）氧化还原电对的一些信息。少

A compact, stainless steel glove box has bee prepared. The main and side chambers can be independently evacuated and then filled with inert gas. The main chamber has inlet and outlet for circulating cooling water. As the differential pressure in the main chamber is often changed with the use of organic materials and for loading something not be resisted in vacuum, the inert gas can be contaneously passed through two chambers. The apparatus for handling cyclopentadienyl compounds and electrochemical studies were prepared to be assembled in the main chamber.The dimer dicyclopentadiene was depolymerized, and the resulting cyclopentadiene was distillled and stocked in a freezing box to prevent the repolymerization prior to use. In a three-necked flask, equipped with a reflux condensor and a capillary for argon gas bubbling, diethylether and pieces of potassium metal were placed, and cyclopentadiene in a limitted amounts was added. After the solvent was evaporated, the potassium complex was … More stocked under vacuum.Uranium peroxide, precipitated from uranyl nitrate solution by the addition of hydrogen peroxide, was filtered and washed and it was converted into amorphous uranium (VI) oxide by heating in air at 400ﾟC.Uranium (IV) chloride, prepared by a reaction of amorphous uranium (VI) oxide with hexachloropropene, was filtered and washed, and it was used for the preparation of tetracyclopentadienyluranium (IV) by a reaction with cyclopentadienyl-potassium in tetrahydrofuran. The excess potassium complex was removed by extraction with n-pentane. The yield of uranium (IV) complex was very low, and an attemped improvement of the yield was still unsuccessful.Another study on the redox reactions of uranium in organic solvents containing tetracyclopentadienyluranium (IV) was carried out by means of cyclic voltammetry. Platinum wires were used as working and counter electrodes, and silver wire was used as a reference electrode. Cyclic voltammogram recorded for uranium (III) /uranium (IV) couple showed the reversibility of the redox couple, and some information conerning uranium (IV) /uranium (V) redox couple was obtained. Less