Ammines of the Lower Chlorides of Titanium
Ammines of the Lower Chlorides of Titanium
复制标题
钛低级氯化物的氨胺
DOI：
10.1021/ja01329a021
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发表时间：
1933
影响因子：
15
通讯作者：
R. Sundström
中科院分区：
文献类型：
--
作者：
W. Schumb;R. Sundström
虽然无水二氯化钛和二氯化钛已经成为许多研究的主题，但关于它们的一些性质的相互矛盾的陈述，以及关于其他性质的数据的缺乏，使得对这些化合物的进一步研究是可取的。特别是，有关这两种氯化物制备的记录观察在某些方面似乎需要修订，而关于这两种物质与氨的反应，我们所知相对较少。本文件的目的是就其中每一个主题提供进一步的资料。Ruff和Neumann通过用各种金属还原四氯化物制备无水氯化物。他们得到了紫色晶体，当在真空中加热时，在425 ℃时开始慢慢升华，并在450 ℃时分解成二氯化物和四氯化物。在475 ℃下，这种分解迅速进行，由此得到的二氯化物对热非常稳定，即使在600 ℃下在真空中也不挥发。值得注意的是，他们无法获得高纯度的样品;他们假设样品在制备过程中会被氧化，从而解释了钛含量高和氯含量低的原因。早期的研究者同样无法获得纯的样品，迈耶和同事们用乔治和斯塔布勒以前使用的冷热管，在高温下用氢气还原四氯化物，制备了四氯化物。在800-1000 ℃时，他们得到二氯化物和三氯化物的混合物，通过在氢气流中加热到300 ℃，
Although anhydrous titanium dichloride and trichloride have been the subject of numerous investigations, conflicting statements relative to some of their properties, and the absence of data concerning others, make the further study of these compounds desirable. In particular, the recorded observations which concern the preparation of the two chlorides appear in some respects to be in need of revision, and comparatively little is known concerning the reactions of these two substances with ammonia. The aim of the present paper is to contribute further information on each of these subjects. Ruff and Neumann1 prepared the anhydrous trichloride by reducing the tetrachloride with various metals. They obtained it as violet crystals, which when heated in a vacuum slowly began to sublime at 425, and to decompose at 450 into the di-and tetrachlorides. At 475 this de-composition proceeded rapidly, and the dichloride thus obtained was very stable to heat and not volatile in a vacuum even at 600. It is interesting to note that they were unable to obtain samples of high purity; they accounted for their high titanium content and low chlorine content by assuming that their samples bad become oxidized during the course of the preparation. Earlier investigators similarly had failed to obtain pure specimens.Meyer and co-workers2 prepared the trichloride by the reduction of the tetrachloride with hydrogen at high temperatures, employing the hot-cold tube previously used by Georges and Stabler. 8 At 800-1000 they ob-tained a mixture of the di-and trichlorides, which was converted com-pletely into the trichloride by heating to 300 in a stream of hydrogen and