锝、铼五配位化合物的构型

摘要: 总结了锝、铼五配位化合物构型的变化规律，并用空腔模型对这些规律进行了解释。铼的五配位化合物皆为高价配合物（氧化态大于四价），在５个配位原子中，当含有１个或５个近距结合原子（带２个或２个以上负电荷的配位原子）时，配合物具有四方锥构型；含有３个近距结合原子时，配合物具有三角双锥构型；含有２个近距结合原子时，配合物具有变形三角双锥构型；含有４个近距结合原子或没有近距结合原子时，五配位结构不稳定。由于锝、铼化学性质相似，这些构型变化规律实际上也是五配位锝化合物的构型变化规律。已测五配位锝化合物的构型种类较少，但都不违反这一构型变化规律。

Abstract: CONFIGURATION OF FIVE COORDINATED RHENIUM AND TECHNETIUM COMPOUNDSLiu Guozheng Liu Boli(Department of Chemistry,Beijing Normal University,Beijing 100875)ABSTRACTThe configuration selection rules of five coordinated rhenium and technetium compounds have been summarized and further rationalized by cavity model.These five coordinated compounds are all of high oxidation state(>+4).If the coordinating atoms are divided into two groups,closecombining atoms with two negative charges or more and normalcombining atoms with one or zero negative charge,the configuration selection rules can be expressed as :(1) systems with five or one closecombining atoms take a square pyramidal configuration;(2) systems with three closecombining atoms take a trigonal bipyramidal configuration;(3) systems with two closecombining atoms take a distorted trigonal bipyramidal configuration;(4) systems with four or none closecombining atoms are unstable and have not been found yet.Key words Configuration Cavity model Five coordinated compounds Rhenium Technetium