The electronic spectra of the hexafluoro complexes of the second and third transition series
The electronic spectra of the hexafluoro complexes of the second and third transition series
复制标题
第二和第三过渡系列六氟配合物的电子光谱
DOI：
--
复制
发表时间：
1974
期刊：
影响因子：
--
通讯作者：
K. D. Warren
中科院分区：
文献类型：
--
作者：
G. C. Allen;K. D. Warren
本工作与我们早先的（1）三维数据处理相结合，构成了对所有过渡金属六氟配合物电子光谱的一个相当完整的调查。一些明显的缺口仍然存在-例如中性六氟化物（MF 6）的4d系列-和更多的数据MF 6 − 5d系列也将是受欢迎的，因为将进一步研究这里处理的一些系统。然而，总的趋势是明确的，在这方面，氟物种的研究已经证明了很大的价值，凭借氟化物配体的能力，以稳定这样一个广泛的氧化态，其中较高的是经常无法在其他系统中访问。一些方面的解释的光谱仍然存在困难，例如分离的中心场和对称性限制的共价效应，在这件事上的光电子能谱和ESCA研究的结果可能会证明是有价值的。因此，对于5d系列的MCl 6 2−阴离子，ESCA研究（94）已经确定，金属上的有效正电荷在整个系列中从左到右减少，正如我们对表25中光谱数据的解释所表明的那样。然而，由此推导出的金属正电荷的大小存在很大的差异，这清楚地表明需要重新考虑通常用于描述这种情况的z eff参数的含义和意义，并且进一步的工作正在朝着这个方向进行。
The present work in conjunction with our earlier (1) treatment of the 3d data constitutes a tolerably complete survey of the electronic spectra of all the transition metal hexafluoro complexes. A number of obvious gaps still remain — for example the neutral hexafluorides (MF6) of the 4d series — and more data for the MF 6 − 5d series would also be welcome, as would further study of some of the systems here treated. The general trends are however clear and in this respect the study of fluoro species has proved of great value by virtue of the ability of the fluoride ligand to stabilise such a wide range of oxidation states, the higher of which are frequently not accessible in other systems. Some aspects of the interpretation of the spectra still present difficulties, for example the separation of central field and symmetry restricted covalency effects, and in this matter the results of photoelectron spectroscopy and ESCA studies may well prove valuable. Thus, for the MCl 6 2− anions of the 5d series ESCA studies (94) have established that the effective positive charge on the metal decreases from left to right across the series, just as suggested by our interpretation of the spectroscopic data in Table 25. There is however a substantial discrepancy in the magnitudes of the metal positive charges thereby deduced, which clearly renders desirable a reconsideration of the meaning and significance of the z eff parameters customarily used to describe such situations, and further work is in progress directed towards this end.