锝化学研究Ⅷ.晶体中锝、铼配合物的构型与键长变化规律

锝化学研究Ⅷ.晶体中锝、铼配合物的构型与键长变化规律

摘要

摘要: 总结了锝、铼化合物中ＭＯ＿６、ＭＯ＿４、ＭＸ＿５ａ和ＭＸ＿４αβ体系中的键长变化规律，并用“空腔模型”予以解释。锝、铼的化学性质非常相似，当体系处于空腔控制状态时，对应化合物具有相同的构型和几乎相等的键长。高价锝、铼易于与Ｎ、Ｏ、Ｆ、Ｓ、Ｃｌ和Ｂｒ结合，而低价锝、铼（≤３价）易于与Ｐ、Ｓｅ等原子结合。处于空腔控制状态的化合物表现出下列性质：（１）ＭＸ＿４αβ体系的赤道平均键长基本不变；（２）ＭＸ＿６体系的平均键长受锝、铼氧化态的影响很小；（３）ＭＸ＿５α体系中Ｍ－α的对位Ｍ－Ｘ键长与赤道偏转角有线性关系。

Abstract: STUDIES OF TECHNETIUM CHEMISTRY Ⅷ.THE REGULARITIES OF THE BOND LENGTH AND CONFIGURATION OF RHENIUM AND TECHNETIUM COMPLEXES IN CRYSTALSLIUGUOZHENG；LIUBOLI（Radio and radiation Chemistry division, Chemistry department,Beijing normal University,Beijing 100875）ABSTRACT Some bond length regularities in MO_6，MO_4，Mx_5a and MX_4αβ moieties of technetium andrhenium compounds are summarized and rationalized by cavity model． The chemical properties oftechnetium and rhenium are so similar that their corresponding complexes have almost the sameconfiguration and M-Xbaond lengths when they are in cavity－controlled state. Technetium andRhenium combine preferably with N，O，F，S，Cl and Br when they are in higher oxidation states（＞3），but preferably with P，Se etc. when they are in lower oxidation states（＜3）．For cavity-controlled coordination compounds of technetium and rhenium，the following bond length regular-ities are manifested：（1）the average equatorial M-Xbond length of MX_4αβis approximatelyconstant;（2）the average M-Xbond length of MX_6 varies moderately with the oxidation state ofM；（3）the bond length of M-Xtrans to M-a in MX_5a has a linear relationship with the angle Key words Average bond length Transeffect Technetium Rhenium Structure

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